Alkoxylation using heterogeneous calcium catalysts and products therefrom

ABSTRACT

This invention relates to heterogeneous (organic polymer-supported) calcium-containing catalysts and the use thereof in the preparation of alkoxylation products, i.e., condensation reaction products of alkylene oxides and organic compounds having at least one active hydrogen. In another aspect of this invention, processes are provided for preparing heterogeneous (organic polymer-supported) calcium-containing catalysts for alkoxylation using calcium oxide or calcium hydroxide as sources for the catalytically-active calcium. In a further aspect of this invention, alkoxylation products are provided that have beneficial, narrow molecular weight ranges and are essentially neutral in pH and free from catalyst residues.

BRIEF SUMMARY OF THE INVENTION

1. Technical Field

This invention relates to heterogeneous (organic polymer-supported)calcium-containing catalysts and the use thereof in the preparation ofalkoxylation products, i.e., condensation reaction products of alkyleneoxides and organic compounds having at least one active hydrogen. Inanother aspect of the invention, processes are provided for preparingheterogeneous (organic polymer-supported) calcium-containing catalystsfor alkoxylation using calcium oxide or calcium hydroxide as sources forthe catalytically-active calcium. In a further aspect of the invention,alkoxylation products are provided that have beneficial, narrowmolecular weight ranges and are essentially neutral in pH and free fromcatalyst residues. These alkoxylation products can be prepared usinghetergeneous, modified calcium-containing catalysts.

2. Background of the Invention

A variety of products such as surfactants, functional fluids, glycolethers, polyols, and the like, are commercially prepared by thecondensation reaction of alkylene oxides with organic compounds havingat least one active hydrogen, generally, in the presence of an alkalineor acidic catalyst. The types and properties of the alkoxylationproducts depend on, among other things, the active hydrogen compound,the alkylene oxide, and the mole ratio of alkylene oxide to organiccompound employed, as well as the catalyst. As a result of thealkoxylation, a mixture of condensation product species are obtainedhaving a range of molecular weights.

In many applications of alkoxylated products, certain of thealkoxylation species provide much greater activity than others.Consequently, alkoxylation processes are desired that are selective tothe production of those alkoxylation species. Further, for many of theseuses, mixtures of alkoxylation products falling within a narrow range ofmolecular distribution of reacted alkylene oxide are believed to besuperior to alkoxylation products in which a single alkoxylation speciepredominates. For example, in a surfactant composition the range ofmaterials on which the surfactant will be required to operate willnormally vary. A range of alkoxylation species, even though narrow, willenhance the performance of the surfactant to the variety of materialswhich it may encounter. Further, mixtures of closely relatedalkoxylation species can provide a mixture having other improvedproperties such as in respect to cloud point, freezing point, pour pointand viscosity as compared to a single specie. There, however, is abalance, and if the distribution of species becomes too broad, not onlyare less desirable alkoxylation species diluting the mixture, but alsothe more hydrophilic or lipophilic components than those in the soughtrange can be detrimental to the sought properties.

Moreover, a wide range of alkoxylation species can restrict theflexibility in ultimate product formulation using the alkoxylationreaction product. For example, in making oil-in-water emulsion productsit is often desired to prepare a concentrated composition that minimizesthe weight percent of water. This concentrate may then be diluted withwater at the time of use, thereby saving the expense of shipping andstoring water. The ability to form a desirable concentrate is generallydependent, in part, on having a narrow distribution of alkoxylationspecies since if heavier moieties are present, a reactor portion ofwater is usually required otherwise gelling (evidencing productinstability) may occur.

The recognition that certain distributions of moles of alkylene oxide tomoles of organic compound in alkoxylation products can be important haslong been recognized. For example, British Patent Specification No.1,399,966 discloses the use of ethoxylates having ahydrophilic-lipophilic balance (HLB) of from about 10 to about 13.5 foruse in a laundry detergent. In order to provide this HLB, the moles ofethylene oxide reacted per mole of fatty alcohol is described as beingcritical. In British Patent Specification No. 1,462,133, the soughtcleaning composition employed alkylene oxide cosurfactants sufficient toprovide even a narrower HLB, i.e., from about 10 to about 12.5. InBritish Specification No. 1,462,134, a detergent composition isdisclosed which uses ethoxylates having an HLB of from about 9.5 to11.5, with the preferred ethoxylates having an HLB of 10.0 to 11.1.

Thus, with the increased understanding of the properties to be providedby an alkoxylation product, greater demands are placed on tailoring themanufacture of the alkoxylation product to enhance the soughtproperties. Accordingly, efforts have been expended to providealkoxylated products in which the distribution of reacted alkylene oxideunits per mole of organic compound is limited to a range in which thesought properties are enhanced.

Alkoxylation processes are characterized by the condensation reaction inthe presence of a catalyst of at least one alkylene oxide with at leastone organic compound containing at least one active hydrogen. Perhapsthe most common catalyst is potassium hydroxide. The products made usingpotassium hydroxide, however, generally exhibit a broad distribution ofalkoxylate species. See, for example, M. J. Schick, NonionicSurfactants, Volume 1, Marcel Dekker, Inc., New York, N.Y. (1967) pp. 28to 41. That is, little selectivity to particular alkoxylate species isexhibited, especially at higher alkoxylation ratios. For example, FIG. 6of U.S. Pat. No. 4,223,164 depicts the distribution of alkoxylatespecies prepared by ethoxylating a fatty alcohol mixture with 60 weightpercent ethylene oxide using a potassium catalyst.

The distribution that will be obtained in alkoxylation processes canvary even using the same type of catalyst depending upon the type oforganic compound being alkoxylated. For example, with nonylphenol, aPoisson type distribution can be obtained using a potassium hydroxidecatalyst. However, with aliphatic alcohols such as decanol, dodecanol,and the like, the distribution is even broader. These distributions arereferred to herein as "Conventional Broad Distributions".

Acidic catalysts can also be used, and they tend to produce a narrower,and thus more desirable, molecular weight distributions; however, theyalso contribute to the formation of undesired by-products and, thus, arenot in wide use commercially.

Particular emphasis has been placed on controlling molecular weightdistribution of alkoxylation products. One approach has been to stripundesirable alkoxylate species from the product mixture. For instance,U.S. Pat. No. 3,682,849 discloses processes for the vapor phase removalof unreacted alcohol and lower boiling ethoxylate components. Thecompositions are said to contain less than about 1% of each of nonethoxylated alcohols and monoethoxylates, less than 2% by weight ofdiethoxylates and less than 3% by weight of triethoxylates. This processresults in a loss of raw materials since the lower ethoxylates areremoved from the composition. Also, the stripped product still has awide distribution of ethoxylate species, i.e., the higher molecularweight products are still present in the composition to a significantextent. To circumvent viscosity problems which would normally exist withstraight-chain alcohols, about 20 to 30 percent of the starting alcoholis to be branched according to the patent.

Obtaining a narrower distribution of alkoxylated species at lowerepoxide reactant to organic compound mole ratios can be readilyaccomplished. U.S. Pat. No. 4,098,818 discloses a process in which themole ratio of catalyst (e.g., alkali metal and alkali metal hydride) tofatty alcohol is about 1:1. Ethoxylate distributions are disclosed forParts C and D of Example 1 and are summarized as follows:

    ______________________________________                                                        Part C    Part D                                              ______________________________________                                        Primary fatty alcohol                                                                           12 carbons  12 to 14                                                                      carbons                                         Moles of ethylene oxide                                                       per mole of alcohol                                                                             3.5         3                                               Product molecular                                                             weight            352         311                                             Average ethoxylation                                                                            3.8         2.54                                            Distribution, %                                                               E.sub.0           0.7         3.8                                             E.sub.1           6.3         15.3                                            E.sub.2           17.3        25.9                                            E.sub.3           22.4        23.8                                            E.sub.4           21.2        15.9                                            E.sub.5           15.6        10.7                                            E.sub.6           8.6         3.5                                             E.sub.7           5.6         1.2                                             E.sub.8           2.3         --                                              ______________________________________                                    

The high catalyst content in combination with the low alkylene oxide toalcohol ratio appears to enable a narrow, low ethoxylate fraction to beproduced. However, as the ratio of alkylene oxide to alcohol increases,the characteristic, Conventional Broad Distribution of alkali metalcatalysts can be expected. Moreover, even though the disclosed processis reported to provide a narrower distribution of ethoxylate species,the distribution is skewed so that significant amounts of the higherethoxylates are present. For example, in Part C, over 15 percent of theethoxylate compositions had at least three more oxyethylene groups thanthe average based on the reactants, and that amount in Part D is over 16percent.

European Patent Application No. A0095562, published Dec. 12, 1983,exemplifies the ability to obtain high selectivity to low ethoxylatespecies when low ratios of ethylene oxide reactant to alcohol areemployed as well as the tendency to rapidly loose that selectivity whenhigher ethoxylated products are sought. For instance, Example 1,(described as a 1 mole EO adduct), which reports the use of adiethylaluminum fluoride catalyst, employs 300 grams of a 12 to 14carbon alcohol and 64 grams of ethylene oxide and Example 5, (describedas a 1.5 mole EO adduct) using the same catalyst, employs a weight ratioof alcohol to ethylene oxide at 300:118. Based on the graphicallypresented data, the distributions appear to be as follows:

    ______________________________________                                                  Example 1                                                                             Example 5                                                   ______________________________________                                        E.sub.0     27        10                                                      E.sub.1     50        36                                                      E.sub.2     17        33                                                      E.sub.3     4         16                                                      E.sub.4     --        6                                                       E.sub.5     --        2                                                       E.sub.6     --        1                                                       ______________________________________                                    

Even with a small increase in ethoxylation from the described 1 mole EOadduct to the described 1.5 mole adduct, the distribution of ethoxylatespecies broadened considerably with more of the higher ethoxylates beingproduced as can be expected from a Conventional Broad Distribution. Itmay be that the catalyst is consumed in the reaction process so that itis not available to provide the narrower distributions of alkoxylationproduct mixtures at the high adduct levels.

Several catalysts have been identified that are reported to providemolecular weight distributions for higher ethoxylates that are narrowerthan those expected from a Conventional Broad Distribution. Inparticular, this work has emphasized ethoxylation catalysis byderivatives of the Group IIA alkaline earth metals. Interest in thesecatalysts, which to date has been confined almost exclusively to theproduction of non-ionic surfactants, stems from their demonstratedcapability for providing hydrophobe ethoxylates having narrowermolecular weight distributions, lower unreacted alcohol contents, andlower pour points than counterparts manufactured with conventionalalkali metal-derived catalysts.

Recently, Yang and coworkers were granted a series of U.S. patents whichdescribe primarily the use of unmodified or phenolic-modified oxides andhydroxides of barium and strontium as ethoxylation catalysts forproducing non-ionic surfactants exhibiting lower pour points, narrowermolecular weight distributions, lower unreacted alcohol contents andbetter detergency than counterpart products prepared by state-of-the-artcatalysis with alkali metal hydroxides. See U.S. Pat. Nos. 4,210,764;4,223,164; 4,239,917; 4,254,287; 4,302,613 and 4,306,093. Significantly,these patents contain statements to the effect that the oxides and/orhydroxides of magnesium and calcium do not exhibit catalytic activityfor ethoxylation, although they may function in the role of promotersfor the barium and strontium compounds (U.S. Pat. No. 4,302,613).

The molecular weight distributions of the ethoxylates disclosed in thesepatents, while being narrower than conventional distributions, appearnot to meet fully the desired narrowness. For example, FIG. 6 of U.S.Pat. No. 4,223,146 depicts the product distribution of an ethoxylate ofa 12 to 14 carbon alcohol and 60 percent ethylene oxide using variouscatalysts. A barium hydroxide catalyst is described as providing aproduct mixture containing, as the most prevalent component, about 16percent of the six mole ethoxylate. The distribution is, however, stillrelatively wide in that the ethoxylate species having three or moreoxyethylene groups than the most prevalent component is above about 19weight percent of the mixture and the distribution is skewed towardhigher ethoxylates. The strontium hydroxide catalyst run which is alsodepicted on that figure appears to have a more symmetrical distributionbut the most prevalent component, the seven mole ethoxylate, is presentin an amount of about 14.5 weight percent and about 21 weight percent ofthe composition had three or more oxyethylene groups than the mostprevalent component.

Also, U.S. Pat. No. 4,239,917 discloses ethoxylate distributions usingbarium hydroxide catalyst and a fatty alcohol. FIG. 7 of that patentillustrates the distribution at the 40 percent ethoxylation level withthe four mole ethoxylate being the most prevalent component. Over about19 weight percent of the mixture has three or more oxyethylene groupsthan the most prevalent component. FIG. 4 depicts the distribution ofethoxylation at the 65 percent ethoxylation level. The nine and ten moleethoxylates are the most prevalent and each represent about 13 weightpercent of the composition. The distribution is relatively symmetricalbut about 17 weight percent of the composition has at least three moreoxyethylene groups than the average peak (9.5 oxyethylene groups).Interestingly, comparative examples using sodium hydroxide catalyst aredepicted on each of these figures and evidence the peaking that can beachieved with conventional base catalysts at low ethoxylation levels,but not at higher ethoxylation levels.

McCain and co-workers have published a series of European patentapplications describing the catalytic use of basic salts of alkalineearth metals especially calcium, which are soluble in the reactionmedium. These applications further disclose catalyst preparationprocedures involving alcohol exchange in respect to the alkoxy moiety ofthe metal alkoxide catalytic species. See European patent publicationNos. 0026544, 0026547, and 0026546, all herein incorporated byreference. See also U.S. Ser. No. 454,560, filed Dec. 30, 1982(barium-containing catalyst) and now abandoned. These workers have alsodisclosed the use of strong acids to partially neutralize and therebypromote the catalytic action of certain alkaline earth metalderivatives. See U.S. Ser. No. 370,204, filed Apr. 21, 1982 and now U.S.Pat. No. 4,453,022, and Ser. No. 454,573 filed Dec. 30, 1982(barium-containing catalyst) and now U.S. Pat. No. 4,453,023, bothherein incorporated by reference. These workers also tend to confirmYang's findings as to calcium oxide, in that McCain et al. teach thatcalcium oxide does not form a lower alkoxide when treated with ethanol.

In particular, calcium metal or calcium hydride is typically thestarting material used by McCain et al. to make the calcium-containingcatalyst. These starting materials, however, are expensive.Consequently, a desire exists to use commonly found sources of calcium,such as calcium oxide (quicklime) and calcium hydroxide (slaked lime),to make calcium-containing catalysts for alkoxylation. Moreover,quicklime and slaked lime are by far the cheapest, most plentiful, leastnoxious, and most environmentally-acceptable of all the alkaline earthmetal derivatives.

The calcium-containing catalysts disclosed by McCain et al. provideenhanced selectivities to higher alkoxylate species as compared tomixtures produced using conventional potassium hydroxide catalyst.Indeed, bases exist to believe that these calcium-containing catalystsprovide narrower distributions of alkoxylates than those provided bystrontium- or barium-containing catalysts. However, there is still needfor improvement in providing a narrower yet distribution of alkoxylationproducts, particularly a distribution in which at least one componentconstitutes at least 20 weight percent of the composition andalkoxylation products having more than three alkoxyl groups than theaverage peak alkoxylation component comprise very little of the productmixture.

Copending U.S. patent application Ser. No. 621,991, filed June 22, 1984and now abandoned, herein incorporated by reference, relates toprocesses for preparing alkoxylation mixtures having relatively narrowalkoxylation product distributions using modified, calcium-containingcatalysts. Processes are also disclosed for making alkoxylationcatalysts using calcium oxide and/or calcium hydroxide as sources forthe catalytically-active calcium. The alkoxylation product mixturesdisclosed therein have a narrow and balanced distribution ofalkoxylation species. The disclosed product mixtures are relatively freefrom large amounts of substantially higher alkoxylation moieties, i.e.,those having at least three more alkoxyl groups than the average peakalkoxylate specie. It is stated therein that narrow distributions can beobtained where the most prevalent alkoxylation moiety has four orgreater alkoxy units, that is, in the regions in which conventionalcatalysts provide a relatively wide range of alkoxylation species.

DISCLOSURE OF THE INVENTION

This invention relates to novel heterogeneous (organicpolymer-supported) alkoxylation catalysts and to processes for makingthe heterogeneous (organic polymer-supported) alkoxylation catalystsusing calcium oxide and/or calcium hydroxide as sources for thecatalytically-active calcium. This invention further relates to novelalkoxylation product mixtures having relatively narrow alkoxylationproduct distributions and negligible amounts of catalyst residues andalso to processes for preparing the alkoxylation product mixtures usingheterogeneous (organic polymer-supported), modified calcium-containingcatalysts.

The heterogenous alkoxylation catalysts of this invention are supportedon a crosslinked organic polymer substrate and characterized by thestructural feature that the calcium atom is chemically bonded to acrosslinked, microporous, macroporous or physically expanded polymericsupport through a carbocyclic or heterocyclic linkage as illustrated bythe following formula:

    R.sub.1 --R.sub.2 --X.sub.1 --Ca--X.sub.2 --R.sub.3        (i)

wherein:

R₁ is an organic polymeric residue which has a crosslinked, microporous,macroporous or physically expanded structure;

R₂ is a carbocyclic or heterocyclic residue;

X₁ and X₂ are independently oxygen or sulfur; and

R₃ is hydrogen or an organic residue of an organic compound having atleast one active hydrogen.

In a preferred aspect of this invention, the heterogeneous alkoxylationcatalysts of formula (i), including the alcohol-exchanged derivativesthereof as described hereinafter, are modified by partial neutralizationwith an inorganic oxyacid having a multivalent anion such as sulfuricacid, phosphoric acid, carbonic acid, pyrosulfuric acid and the like, orby metal salts of the inorganic oxyacids such as aluminum sulfate, zincsulfate, zinc phosphate and the like. The inorganic oxyacids and themetal salts thereof are at times referred to hereinafter as "modifiers".These partially neutralized catalysts are believed to have complexstructures which are probably comprised of a mixture of species, certainof which may not even be catalytically active. Those species which arecatalytically active are believed to have structures of the typedepicted by the following formula:

    [R.sub.1 --R.sub.2 --X.sub.1 --Ca].sub.f Y.sub.1 [Ca--X.sub.2 --R.sub.3 ].sub.g                                                   (ii)

wherein R₁, R₂, R₃, X₁ and X₂ are as defined hereinabove, Y₁ is amultivalent oxyacid anion of valence 2 to 4 and f and g are integershaving a value such that the sum f+g is equal to the valence of Y₁. Itis understood that formula (ii) is speculation only.

Another aspect of the invention provides a method for preparing aheterogeneous (organic polymer-supported) alkoxylation catalyst, whichmethod comprises (i) preparing a catalyst precursor by reacting anorganic polymer which has a crosslinked, microporous, macroporous orphysically expanded structure with a carbocyclic or heterocycliccompound, (ii) solubilizing, at least in part, calcium oxide and/orcalcium hydroxide, or mixtures thereof, by mixing any of them with anactivator to form a calcium containing composition having titratablealkalinity, and (iii) reacting the catalyst precursor with thecalcium-containing composition under effective reaction conditions toproduce the alkoxylation catalyst. The term "solubilizing" as usedherein is intended to mean that the calcium is provided in an activeform which is not the case when calcium is in the form of calcium oxideor calcium hydroxide, hence a solubilization is believed to exist;however, the term is not intended to be limiting to the formation of atruly dissolved calcium specie (which may or may not exist).

The solubilization is effected by mixing any of calcium oxide andcalcium hydroxide with an activator having the general formula Z_(a)--X--Q--Y--Z'_(b) wherein X and Y are the same or differentelectronegative (relative to carbon), hetero (i.e., non-carbon) atomsselected from the group consisting of oxygen, nitrogen, sulfur andphosphorous; a and b are the same or different integers satisfying thevalency requirements of X and Y; Q is any organic radical which iselectropositive or essentially neutral relative to X and/or Y, whichdoes not prevent the solubilization, and which contains at least onecarbon atom and preferably has the formula ##STR1## wherein R₄ and R₅are the same or different and are selected from the group consisting ofhydrogen and lower alkyl or alkylene groups of one to four carbon atoms,and p is an integer from 1 to 6, preferably 2 to 4; Z and Z' are thesame or different and are either hydrogen or an organic radical whichdoes not interfere with the function of the activator for its intendedpurpose, i.e., its solubilizing function, thereby forming acalcium-containing composition which is then reacted with the catalystprecursor to produce an essentially solid catalyst which iscatalytically active in the alkoxylation of compounds having activehydrogens, especially alcohols.

Solubilization of calcium oxide or calcium hydroxide results in theproduction of an alkaline slurry, which alkalinity can be detected andmeasured by titration and which is referred to herein as "titratablealkalinity".

The heterogeneous catalyst composition can be directly contacted withalkylene oxides to form alkoxylates of the activator itself, if havingan active hydrogen, to produce alkoxylates. If the activator does nothave an active hydrogen, excess activator should preferably be removedprior to alkoxylation.

According to further embodiments of this aspect of the invention, anexchange reaction is carried out after the reaction of thecalcium-containing composition with the catalyst precursor underconditions at which an exchange reaction will occur, with at least oneorganic compound having an active hydrogen, e.g., an alcohol, having ahigher boiling point (and usually a longer carbon chain length) thansaid activator to form the corresponding, catalytically active higherboiling derivative of calcium. This latter catalytic species can then bedirectly contacted with alkylene oxide to form alkoxylates of the higherboiling material.

The alkoxylation processes of this invention involve the condensationreaction of an alkylene oxide and at least one organic compound havingat least one active hydrogen in the presence of a catalyticallyeffective amount of a heterogeneous (organic polymer-supported),modified calcium-containing catalyst as described above. Theheterogeneous modified catalyst comprises a strong, inorganic oxyacidprovided in an amount of about 0.2 to 0.9, e.g., 0.35 to 0.85, often,about 0.45 to 0.75, times that required to neutralize the catalystcomposition, which is sufficient to narrow the distribution of thealkoxylation product mixture and provide at least one alkoxylationspecie in an amount of at least about 20 weight percent of the mixture.In addition, alkoxylation products are provided which are essentiallyneutral in pH and free from catalyst residues. The heterogeneousmodified catalyst is prepared under sufficient agitation to ensure arelatively uniform product. The preferred oxyacid is sulfuric acid.Frequently, the heterogeneous modified catalyst is prepared in a mediumhaving a dielectric constant at 25° C. or its normal boiling point,whichever is less, of at least about 10, preferably, at least about 20,say, about 20 to 50, and frequently about 25 or 30 to 45.

By this invention, alkoxylation product mixtures are provided which havea narrow, but balanced distribution of alkoxylation species. Theseproduct mixtures are relatively free from large amounts of substantiallyhigher alkoxylation moieties, i.e. those having at least three morealkoxyl groups than the average peak alkoxylate specie. Advantageously,these narrow distributions can be obtained where the most prevalentalkoxylation moiety has four or greater alkoxy units, that is, in theregions in which conventional catalysts provide a relatively wide rangeof alkoxylation species. The product mixtures are essentially neutral inpH and contain negligible amounts of catalyst residues, therebyrequiring no post-treatment.

The alkoxylation product mixtures prepared by the processes of thisinvention are characterized as the condensation reaction products ofalkylene oxides and organic compounds having at least one activehydrogen in which the mole ratio of reacted alkylene oxide per activehydrogen is at least about 4, say, about 4 to 16 or 24, preferably about5 to 12. The product mixtures have at least one alkoxylation moietywhich constitutes at least about 20, say, about 20 to 30 or 40, and mostoften about 20 to 30, weight percent of the composition. Thealkoxylation mixtures of this invention also have a relativelysymmetrical distribution. Hence, the portion of the product mixturehaving three or more oxyalkylene unit groups (per active hydrogen siteof the organic compound) than the peak alkoxylation specie is relativelyminor, e.g., often less that about 12, say, less than 10, and oftenabout 1 to 10, weight percent of the mixture. Similarly, thealkoxylation species having fewer oxyalkylene groups (per activehydrogen site of the organic compound) by three or more oxyalkylenegroups from the average peak alkoxylation specie is usually relativelyminor, e.g., less than about 15, say, less than about 10, often about0.5 to 10, weight percent of the composition. Generally, the oneoxyalkylene unit higher and the one oxyalkylene unit lower alkoxylatesin respect to the most prevalent alkoxylation specie are present in aweight ratio to the most prevalent alkoxylation specie of about 0.6:1 to1:1.

The preferred alkoxylation product mixtures of this invention correspondto the formula

    P.sub.n =A×e.sup.-(n-n)/2.6+0.4n

wherein n is the number of oxyalkylene groups per reactive hydrogen sitefor an alkoxylation specie (n must equal at least one) of thecomposition, n is the weight average oxyalkylene number, A is the weightpercent of the most prevalent alkoxylation specie in the mixture andP_(n) is, within plus or minus two percentage points, the weight percentof the alkoxylation specie having n oxyalkylene groups (per activehydrogen site) in the mixture. This distribution relationship generallyapplies where n is between the amount of n minus 4 to the amount of nplus 4.

For purposes herein, the average peak alkoxylation specie is defined asthe number of oxyalkylene groups (per active hydrogen site) of the mostprevalent alkoxylation specie when the next higher and lower homologsare each present in a weight ratio to the most prevalent alkoxylationspecie of less than 0.9:1. When one of the adjacent homologs is presentin a weight ratio greater than that amount, the average peakalkoxylation specie has an amount of oxyalkylene groups equal to thenumber average of those of the two species. The weight averageoxyalkylene number is the weight average of the oxyalkylene groups ofthe alkoxylation species in the mixture (including unreacted alcohol),i.e., n equals the sum of (n)(P_(n)) for all the species present dividedby 100.

Preferred alkoxylation product mixtures of this invention includepoly(oxyethylene)glycols, i.e., CARBOWAX®, and fatty alcoholethoxylates, i.e., TERGITOL®. CARBOWAX® is the registered trademark ofUnion Carbide Corporation for a series of poly(oxyethylene)glycols.Ethylene glycol can be used to make the CARBOWAX®poly(oxyethylene)glycols or the CARBOWAX® poly(oxyethylene)glycols canbe used to make higher molecular weight CARBOWAX®poly(oxyethylene)glycols. For example, CARBOWAX® poly(oxyethylene)glycol200 can be used to make CARBOWAX® poly(oxyethylene)glycol 400.Specifically, the CARBOWAX® poly(oxyethylene)glycols are liquid andsolid polymers of the general formula H(OCH₂ CH₂)_(w) OH, where w isgreater than or equal to 4. In general, each CARBOWAX®poly(oxyethylene)glycol is followed by a number which corresponds to itsaverage molecular weight. Generally, the invention process is notpreferred for using CARBOWAX® poly(oxyethylene)glycols having an averagemolecular weight above about 600 to 800 as starting materials becausesuch CARBOWAX® poly(oxyethylene)glycols are solids at room temperature(although they are liquid at the reaction temperatures, e.g., 110° C.).Examples of useful CARBOWAX® poly(oxyethylene)glycols are: CARBOWAX®poly(oxyethylene)glycol 200, which has an average w value of 4 and amolecular weight range of 1 90 to 210; CARBOWAX® poly(oxyethylene)glycol400, which has an average w value between 8.2 and 9.1 and a molecularweight range of 380 to 420; and CARBOWAX® poly(oxyethylene)glycol 600,which has an average w value between 12.5 and 13.9 and a molecularweight range of 570 to 630.

TERGITOL® is the registered trademark of Union Carbide Corporation for aseries of ethoxylated nonylphenols, primary and secondary alcohols,i.e., nonionic surfactants, and the sodium salts of the acid sulfate ofsecondary alcohols of 10 to 20 carbon atoms, i.e., anionic surfactants.Examples of the TERGITOL® nonionic surfactants include TERGITOL® SNonionics which have the general formula CH₃ (CH₂)_(x) CH(CH₃)--O--(CH₂CH₂ O)_(y) H wherein x is a value of 9-11 and y is a value of aboutgreater than 1. Examples of the TERGITOL® anionic surfactants includeTERGITOL® Anionic 08, which is C₄ H₉ CH(C₂ H₅)CH₂ SO₄ --Na; TERGITOL®Anionic 4, which is C₂ H₉ CH(C₂ H₅)C₂ H₄ CH--(SO₄ Na)CH₂ CH(CH₃)₂ ; andTERGITOL® Anionic 7, which is C₄ H₉ CH(C₂ H₅)C₂ H₄ CH--(SO₄ Na)C₂ H₄CH(C₂ H₅)₂.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 depicts the average ethoxylate distribution for fatty alcoholethoxylates prepared in Example 11 hereinafter (supported CaO/H₂ SO₄) aswell as unsupported CaO, unsupported KOH and unsupported CaO/H₂ SO₄. Theaverage ethoxylate distributions were obtained by averaging (area %values) individual gas chromatography scans.

FIG. 2 depicts the average ethoxylate distribution forpoly(oxyethylene)glycols prepared in series 1 and series 2 of Example 12hereinafter (supported CaO) as well as unsupported Ca(OH)₂ andunsupported KOH. The average ethoxylate distributions were obtained byaveraging (area % values) individual gas chromatography scans.

FIG. 3 depicts the average ethoxylate distribution forpoly(oxyethylene)glycols prepared in Example 9, Part B, hereinafter(supported CaO) as well as unsupported KOH and unsupported CaO. Theaverage ethoxylate distributions were obtained by averaging (area %values) individual gas chromatography scans.

FIG. 4 depicts the average ethoxylate distribution forpoly(oxyethylene)glycols prepared in Example 9, Part C, hereinafter(supported CaO) as well as unsupported KOH and unsupported CaO. Theaverage ethoxylate distributions were obtained by averaging (area %values) individual gas chromatography scans.

FIG. 5 depicts the average ethoxylate distribution forpoly(oxyethylene)glycols prepared in Example 9, Part A, hereinafter(supported CaO) as well as unsupported KOH and unsupported CaO. Theaverage ethoxylate distributions were obtained by averaging (area %values) individual gas chromatography scans.

DETAILED DESCRIPTION

The organic polymer-supported calcium-containing catalysts of thisinvention are heterogeneous catalysts, that is, they are useful inheterogeneous catalysis. Heterogeneous catalysis involves a catalyticreaction in which the reactants and the catalyst comprises two separatephases, e.g., gases over solids, or liquids containing finely-dividedsolids as a disperse phase. By way of contrast, homogeneous catalysisinvolves a catalytic reaction in which the reactants and the catalystcomprise only one phase, e.g., an acid solution catalyzing other liquidcomponents. The alkoxylation reactions of this invention occur on thesurface of the solid catalyst particles. The individual steps ofheterogeneous catalytic processes probably involve the following: (1)diffusion of reactants to surface; (2) adsorption of reactants onsurface; (3) reaction of adsorbed reactant to form adsorbed product; (4)desorption of product; and (5) diffusion of product into main stream ofa liquid or vapor.

As indicated above, the heterogeneous alkoxylation catalysts of thisinvention are supported on a crosslinked organic polymer substrate andcharacterized by the structural feature that the calcium atom ischemically bonded to a crosslinked, microporous, macroporous orphysically expanded polymeric support through a carbocyclic orheterocyclic linkage as illustrated by the following formula:

    R.sub.1 --R.sub.2 --X.sub.1 --Ca--X.sub.2 --R.sub.3        (i)

wherein:

R₁ is an organic polymeric residue which has a crosslinked, microporous,macroporous or physically expanded structure;

R₂ is a carbocyclic or heterocyclic residue;

X₁ and X₂ are independently oxygen or sulfur; and

R₃ is hydrogen or an organic residue of an organic compound having atleast one active hydrogen.

In a preferred aspect of this invention, the heterogeneous alkoxylationcatalysts of formula (i), including the alcohol-exchanged derivativesthereof, are modified by partial neutralization with an inorganicoxyacid having a multivalent anion such as sulfuric acid, phosphoricacid, carbonic acid, pyrosulfuric acid and the like, or by metal saltsof the inorganic oxyacids such as aluminum sulfate, zinc sulfate, zincphosphate and the like. These partially neutralized catalysts arebelieved to have complex structures which are probably comprised of amixture of species, certain of which may not even be catalyticallyactive. Those species which are catalytically active are believed tohave structures of the type depicted by the following formula:

    [R.sub.1 --R.sub.2 --X.sub.1 --Ca].sub.f Y.sub.1 [Ca--X.sub.1 --R.sub.3 ].sub.g                                                   (ii)

wherein R₁, R₂, R₃, X₁ and X₂ are as defined hereinabove, Y₁ is amultivalent oxyacid anion of valence 2 to 4 and f and g are integershaving a value such that the sum f+g is equal to the valence of Y₁. Itis understood that formula (ii) is speculation only.

The alkoxylation product mixtures of this invention ar enabled by theuse of heterogeneous (organic polymer-supported) calcium-containingcatalysts that have been modified by strong, inorganic oxyacids or metalsalts thereof sufficient to provide a defined narrow distribution ofalkoxylation products. The alkoxylation conditions may otherwise varywhile still obtaining a narrower distribution of alkoxylate products.

The modifier of the catalyst is preferably a polyvalent acid andcontains at least one, most often at least about 2, oxygen atoms thatare conventionally depicted as double bonded to the nucleus atom. Suchacids include, for example, sulfuric and phosphoric acid; however, ingeneral the most narrow distributions are obtained using sulfuric acid.

The amount of modifier employed and the manner in which it is introducedto prepare the catalyst can be determinative of whether the desirednarrow distribution with at least one alkoxylation specie being presentin an amount of at least about 20 weight percent of the composition, isachieved. While not wishing to be limited to theory, it is believed thatactive catalysts for producing narrow distributions of alkoxylationproducts comprise a calcium atom in association with the modifier anionin a manner in which the calcium atom is activated as illustrated byformula (ii) hereinabove.

In general, at the time of modification, the calcium-containing catalystmay be represented by formula (i) hereinabove wherein --X₂ R₃ is anorganic-containing residue of an organic compound having an activehydrogen, and X₂ is oxygen, nitrogen, sulfur or phosphorous. R₃ may thusalso contain double bonded oxygen (the organic compound was a carboxylicacid), hetero atom such as oxygen, sulfur, nitrogen and phosphorous(e.g., the organic compound was a glycol, polyamine, ether of a glycolor the like). Frequently, R₃ comprises 1 to 20 carbons.

The amount of modifier added is in an amount of about 0.2 to 0.9, say,about 0.45 to 0.75, times that required to neutralize the catalystcomposition. Frequently, the molar ratio of modifier sites (sulfuricacid has two acid sites and phosphoric acid has three acid sites) tocalcium atoms is about 0.5:1 to 1.8:1.

The modifier appears to enable the desired catalytically active calciumspecies to form; however, it has been found that depending upon otherconditions during the modification, different amounts of modifier willprovide the optimum catalyst in terms of selectivity and reaction rateduring an alkoxylation process. Accordingly, an aspect of the inventionis providing a level of modification sufficient to achieve the narrowdistribution of alkoxylate product mixtures.

The medium containing the heterogeneous calcium catalyst can also affectwhether the resulting modified calcium catalyst enables the desirednarrow distribution of alkoxylation products to be formed. If the mediumcomprises as the predominant component, i.e., solvent, a material thathas a low dielectric constant, the modifier can form a separate liquidphase and increased difficulty in obtaining an intimate admixture may beobserved. On the other hand, with solvents that are too polar, theorganic moiety in association with the calcium atom may be displacedwith the solvent. Accordingly, undue amounts of water are typicallyavoided during the modification of the calcium-containing catalyst. Mostoften, the medium and the organic compound providing the moiety on thecalcium atom are the same. Particularly convenient media includeethylene glycol, propylene glycol, diethylene glycol, lycerol,butanediols, 1,3 propanediol, and the like. Conveniently, the mediumemployed, if not intended to be a reactant for producing alkoxylates,should have a sufficiently low boiling point that can readily be removedfrom the catalyst and organic compound reactant mixture by distillation.Most often, the medium comprises a solvent having at least twohetero-atoms such as the activators described herein.

The modifier is preferably added while the calcium-containing catalystis being vigorously agitated. In this regard, a slow addition of themodifier to the calcium-containing catalyst is preferred. Generally,less than 10 percent of the modifier to be added is added to thecalcium-containing catalyst at any one time. The addition of themodifier can be conducted at a convenient temperature. e.g., about 10°C. to 160° C., say, about 50° C. to 150° C. Preferably, a nitrogenatmosphere is advantageous.

The calcium-containing catalyst having a substituent of the formula --X₂R₃ may be prepared in any suitable manner. For example, a catalystprecursor can be prepared by reacting an organic polymer which has acrosslinked, microporous, macroporous or physically expanded structurewith a carbocyclic or heterocyclic compound. Then, calcium metal,hydride or acetylide or other suitable source of calcium may be reactedwith an organic compound containing an active hydrogen atom of theformula HX₂ R₃. With compounds having higher molecular weights, e.g., 4or more carbons, it is generally preferred to use a lower molecularweight and more reactive and volatile compound of the formula HX₂ R₃(e.g., of 1 to about 3 carbons, especially compounds such as ethanol,ethylamine, ethylene glycol and the like) and then exchange thatsubstituent with the higher molecular weight substituent while removingthe lower molecular weight material by volatilization. Alternatively,the calcium-containing catalyst can be prepared from quicklime or slakedlime by the process disclosed hereinafter. The catalyst precursor isthen reacted with the source of the catalytically-active calcium toproduce the heterogeneous alkoxylation catalyst.

The compounds having the formula HX₂ R₃ include those organic compoundshaving active hydrogens described in connection with the alkoxylationproducts of this invention, such as alcohols, phenols, carboxylic acidsand amines. Most often, the compounds having the formula HX₂ R₃ arealcohols. When an exchange reaction is to be conducted to provide ahigher molecular weight substituent on the calcium atom, it is generallypreferred to conduct the acid modification prior to exchange and use alower molecular weight material for the replacement substituent toenhance the acid modification process.

The preparation of the modified calcium catalyst composition fromcalcium metal, hydride or acetylide or other suitable source of calciumis typically conducted at elevated temperatures, e.g., from about 30° C.to 200° C. or more, and in a liquid medium. The organic compound whichprovides the substitution is normally provided in excess of thatrequired for reaction with the calcium reactant. Hence, the weight ratioof calcium to the organic compound frequently is within the range ofabout 0.01:100 to 25:100. The reaction may, if desired, be conducted inthe presence of an inert liquid solvent. The exchange reaction is alsoconducted under elevated temperature and, optionally, under reducedpressure to facilitate removal of the more volatile components.Temperatures may range from about 50° C. to 250° C., say, about 80° C.to 200° C. or 250° C., and pressures (absolute) are often in the rangeof 1 millibar to 5 bars, e.g., about 10 millibars to 2 bars.

It is usually desired that the organic substituent on the modified,calcium-containing catalyst composition correspond to the "starter"component for the alkoxylation process. The starter component is theorganic compound having at least one active hydrogen with which thealkylene oxide reacts.

The alkoxylation is conducted using a catalytically-effective amount ofthe calcium-containing catalyst, e.g., about 0.01 to 10, often about 0.5to 5, weight percent based on the weight of the starter component. Thecatalysts substantially retain their activities during the alkoxylation,regardless of the amount of alkylene oxide employed. Thus, the amount ofcatalyst can be based on the amount of starter provided to thealkoxylation zone and not the degree of alkoxylation to be effected.Moreover, the catalyst can be recovered (since it is a solid) from thereaction product and reused. Indeed, it has been found that conditioned(preused) catalysts may provide superior products. The catalysts alsoappear to be relatively storage stable and are relatively tolerant ofwater. Hence, storage can be effected under convenient conditions.

Normally, the catalyst and the starter component are admixed and thenthe alkylene oxide is added at the reaction temperature until thedesired amount of alkylene oxide has been added, then the product isneutralized and can be finished, if desired, in any procedure includingstripping unreacted starter material from the product mixture,filtration, or further reaction, e.g., to form sulfate.

The temperature of the alkoxylation is sufficient to provide a suitablerate of reaction and without degradation of the reactants or reactionproducts. Often, the temperatures range from between about 50° C. and270° C., e.g. from about 100° C. to 200° C. The pressure may also varywidely, but when low boiling alkylene oxides such as ethylene oxide..andpropylene oxide are employed, a pressurized reactor is preferably used.

The alkoxylation reaction medium is preferably agitated to ensure a gooddispersal of the reactants and catalyst throughout the reaction medium.Also, the alkylene oxide is usually added at a rate approximating thatwhich it can be reacted.

While typically alkoxylation products are neutralized, upon removal ofthe catalysts employed in accordance with the processes of theinvention, the alkoxylation product mixture is relatively neutral, e.g.,about a pH of 6, regardless of the pH of the catalyst containingproduct. Neutralization, however, may assist in the recovery of thecatalyst from the alkoxylation product mixture. When neutralizing, acidsthat may tend to form catalyst-containing gel structures or solids thatclog filtering apparatus should be avoided. Conveniently, sulfuric acid,phosphoric acid, propionic acid, benzoic acid and the like are used.

The present invention provides a procedure whereby calcium oxide(quicklime) and its hydrated form, calcium hydroxide (slaked lime) (bothherein referred to as "lime"), can be effectively used to preparecatalytic species which are active in the alkoxylation of organiccompounds having at least one active hydrogen such as alcohols,especially long-chain fatty alcohols, carboxylic acids, amines, polyolsand phenols. This is accomplished by the following general procedure.

A catalyst precursor is prepared by reacting an organic polymer whichhas a crosslinked, microporous, macroporous or physically expandedstructure with a carbocyclic or heterocyclic compound. To be of utilityas a support for the heterogeneous catalysts of this invention, theorganic polymer should (i) possess a network (crosslinked) structure ofan insoluble, yet solvent-swellable type, (ii) possess microporous,macroporous or physically expanded morphology conferring high surfacearea, low density and liquid permeability, (iii) possess satisfactorychemical, physical and mechanical stability, and (iv) possessfunctionality of an aromatic type or of a precursor type through whicharomatic functionality can be introduced by chemical modification.

A large number and variety of organic polymers can have utility in thepreparation of the polymer-supported calcium catalysts of thisinvention. Such organic polymers are conventional materials known in theart. Two preferred general classes of polymers include the (1)polystyrenics, made by free radical polymerization, and the (2)phenolics, made by condensation polymerization.

A versatile class of organic polymeric supports is the polystyrenepolymers; these polymers, in their simplest form, are copolymers ofstyrene with divinyl benzene wherein the desired degree of crosslinkingis readily controlled by the quantity of divinyl benzene used. Thecopolymers are produced by suspension polymerization techniques whichpermit the products to be formed as spherical beads of controllable size(over a range from about 20-400 mesh) and morphology (microreticular ormicroreticular). Functionalized versions of such resins can be madeeither directly by using the appropriately functionalized styrenemonomer or indirectly by performing appropriate chemical reactions oncopolymers made from styrene itself.

From the standpoint of supported catalyst synthesis efforts, a preferredclass of styrene/divinyl benzene copolymers is that known as Merrifield®Resins, developed by R. Merrifield for use in the polymer-supportedsynthesis of peptides. The Merrifield® Resins are chloromethylatedstyrene/divinyl benzene resins wherein the degree of functionalizationcan be readily controlled. The chloromethyl function is highly reactivewith a broad spectrum of reagents, so that resins having virtually anydesired type of functionality can be obtained from these intermediatesthrough well-characterized chemical transformations. These Merrifield®Resins are preferred materials for preparing the catalyst precursors tothe supported calcium catalysts of the instant invention. Thus,preferred catalyst precursors can be prepared either by alkylating thedesired carbocyclic or heterocyclic compound, e.g., phenol orthiophenol, with a Merrifield® Resin under Friedel-Crafts conditions orby condensing a monoalkali metal salt of the carbocyclic or heterocycliccompound, e.g., diphenol or dithiophenol, with Merrifield® Resin underWilliamson etherification conditions. Many synthetic routes to sucharyloxy- or arylthio-containing resins from the chloromethylated resinmaterials are known in the art.

Another class of polymers which is particularly useful for making thesupported calcium catalysts of this invention is the phenolic resins.These polymers are prepared by condensing phenol or a substituted phenolwith some aldehyde, usually formaldehyde, in the presence of causticunder conditions such that the formaldehyde reactant is in excess. Thiscondition promotes crosslinking, a necessary property of a polymericsupport. The degree of crosslinking can be controlled by the chargeratio of the reactants and a spherical, hollow bead form of the resinknown as microballons can be produced by expanding the curing polymericmass with a gas such as nitrogen released thermally from a chemicalblowing agent in the formulation. These hollow spheres have an extremelylow bulk density and a porous structure which is permeable to, andswollen by, many organic liquids. The spheres are typically of size fromabout 0.005 to 0.15 mm, or about 150 mesh on average. As precursors tothe supported calcium catalysts, these phenolic "microballons" areattractive because (1) they are suitable for calcium loading asreceived, i.e., the aryloxy or arylthio functionality is alreadypresent, (2) they accept high levels of calcium loading, (3) they can befine-tuned for ultimate catalytic activity by using appropriatelysubstituted phenols in the original condensation, (4) they have goodchemical stability, and (5) they are an article of commerce.

There are a large number of conventional synthetic techniques andclassical reactions which can be employed to prepare the catalystprecursors. In the case of the crosslinked polystyrene resins, forexample, the three principal alternative methods for introducing therequired aryloxy or arylthio functionality are:

1. Direct route, wherein the required functionality is performed on themonomer itself and this desirably-functionalized monomer is thencopolymerized with divinylbenzene;

2. Indirect route, wherein the desired functionality is introduced via a"grafting" approach, such as, for example, the Friedel-Crafts reactionof a phenol or thiol with a reactive functionalized resin such as thechloromethylated resins (Merrifield® Resins); and

3. A semi-direct approach, wherein the monomer itself is functionalizedas in the direct route above, but this functionality is of a precursortype requiring post-modification to convert it into the required aryloxyor arylthio functions. Examples of this approach include the use of amethoxystyrene monomer and acid cleavage of the --OCH₃ group in thepolymer to an --OH group or the use of a nitrostyrene monomer followedby reduction, diazotization and hydrolysis of the polymer to convert theoriginal --NO₂ groups into --OH groups.

In the case of phenolic resin type supports, post-modification of theresin is normally not an issue because the required aryloxy or arylthiofunctionality is introduced directly via one of the monomers used in thecondensation polymerization. With such supports, however, chemicalpost-modifications can be employed, if so desired, to modify either theacidity of the --OH or --SH function or its steric environment. It isalso possible, of course, to use mixtures of phenols or thiophenols inthese condensations.

A preferred type of catalyst precursor which can be utilized is one madeby reaction of a crosslinked functionalized polystyrene resin (e.g., thechloromethylated Merrifield® Resins) with a crosslinked, expandedphenolic resin to make a catalyst precursor which is comprised of apolymeric support type resin graft-modified with a polymeric resincontaining the required aryloxy or arylthio functionality. All suchprecursor compositions are intended to be included within the scope ofthis invention without limitations with regard to method of preparation.

The carbocyclic or heterocyclic compound used herein is an importantaspect of this invention. A commercially useful heterogeneous catalystmust exhibit not only an acceptable level of catalytic activity, butalso outstanding chemical and physical stability. These are the minimumqualifications which the catalyst must possess; not surprisingly, thesecond characteristic is frequently more difficult to achieve than thefirst. This is certainly the case in the instant invention. Indeed, animportant aspect of this invention is its definition of a structuralfeature important to the preparation of a chemically stable, supportedcalcium catalyst; that is, a catalyst which does not release calciumions into the reaction medium and, consequently, provides an ethoxylatedproduct which is essentially neutral in pH and free from catalystresidues.

The structural feature which is responsible for imparting this chemicalstability to the catalysts herein described is the carbocyclic orheterocyclic residue, e.g., the phenoxy or thiophenoxy functionality,which serves to bind the metal atom (calcium) to the organic polymericsupport. In the generic formulae (i) and (ii) above this chemicallinkage appears as the --R₂ --X₁ --Ca-- grouping wherein X₁ may beeither oxygen (a phenoxide) or sulfur (a thiophenoxide). The stabilityof the --X₁ Ca-- chemical bond is related to the acidity of the parentphenols and/or thiophenols. As a chemical class, phenols and thiophenolsare relatively weak acids with dissociation constants typically in theorder of 10⁻⁹ to 10⁻¹¹ (pKas of about 9-11). On an acidity scale, thephenols/thiophenols lie about midway between organic (carboxylic) acidswith pKas of about 4 to 6 and aliphatic alcohols with pKas of about14-16. Since the undesirable reaction of calcium release from thesupported catalyst involves attack of some acidic species at the metalatom site on the catalyst with concomitant release of the conjugate acidof R₂ X₁, (i.e., R₂ X₁ H), the --X₁ --Ca-- bond should be stable towardany acidic species whose dissociation constant is substantially belowthat of the R₂ X₁ H species which would be liberated in the calciumrelease process. Accordingly, the X₁ --Ca bond in the --R₂ --X₁ --Ca--function should be stable in the aliphatic alcohol environmentprevailing in typical alkoxylation processes and calcium release fromthe supported catalyst should not occur. The --Ca--X₂ -- bond of--Ca--X₂ --R₃ group, by way of contrast, is unstable toward aliphaticalcohols because the conjugate acid (HX₂ R₃) of --X₂ R₃ which isdisplaced is comparable in pKa to the alcohol(s) comprising thealkoxylation medium. Thus, the process of alkoxide exchange occursfreely around the --Ca--X₂ -- group and normally will continue until therequisite quantity of alkylene oxide monomer has been consumed inproduction of the desired alkoxylate product.

The important role of the carbocyclic or heterocyclic residue, e.g., thearyloxy/arylthio functionality, in the performance of the supportedcalcium catalysts is apparent from the foregoing discussion. Animportant aspect of this invention lies in the definition of thisparticular functionality as important to the successful implementationof the supported calcium alkoxylation catalyst. Whereas the presence ofaryloxy or arylthio functionality is important in the catalysts of thisinvention, there are but few limitations on the types of aryloxy orarylthio species which are suitable for use. The primary limitationimposed upon the aryloxy or arylthio functional group is that itsconjugate acid, i.e., the parent phenol or thiophenol, have adissociation constant falling within the range of 10⁻⁷ to -10¹³, or apKa in the range of 7 to 13. Providing this limitation is met, thearyloxy or arylthio function can be of the monocyclic type, e.g., phenolitself, polycyclic type, e.g., tetralin, indene, flourene, anthracene,etc., or heterocyclic type, e.g., benzofuran, benzopyran, etc. Further,the aryloxy or arylthio function may be substituted with any otherfunctional groups in any number, providing that such substitutionneither causes the dissociation constant of the conjugate acid of thearyloxy or arylthio species to fall outside the 10⁻⁷ to 10⁻¹³ range norinterferes chemically with either the progress of the calcium-loadingreaction or the performance of the finished supported calciumalkoxylation catalyst. The aryloxy or arylthio species may also be ofpolymeric type, e.g., R₂ --OH or R₂ --SH terminated linear polymers suchas that derived from the condensation of hydroquinone with1,2-dibromoethane or that from condensation of 4,4'-biphenol withbis(4-chlorophenyl)sulfone.

Polymeric aryloxy or arylthio species in fact are frequently preferredtypes because, upon reaction with an appropriately functionalizedpolymeric support and subsequent calcium loading, they afford supportedcatalysts having the catalytically active (calcium atoms) sites farremoved from the support itself and, hence, free from steric hinderanceeffects which might reduce catalytic activity.

Lime is then contacted with an activator under conditions at which thelime and the activator will react or interact to form one or morecatalytically active derivatives, hereinafter referred to collectivelyas "the derivative". The activator may be any compound having theformula

    Z.sub.a --X--Q--Y--Z'.sub.b

wherein the various terms are as previously defined. Heterogeneousalkoxylation catalysts incorporating the derivatives of this reactionare especially effective in the alkoxylation of alcohols, particularlyprimary alcohols such as the long-chain fatty alcohols, or mixturesthereof, which are used as starters in the manufacture of nonionicsurfactants. However, heterogeneous alkoxylation catalysts incorporatingthe derivative can also be effectively used in the catalytic reaction ofa wide variety of organic compounds containing active hydrogen. If, forexample, the activator is ethylene glycol, the derivative can readily beutilized in situ to catalyze the alkoxylation of ethylene glycol itself,thereby producing ethylene glycol-started poly(oxyalkylene)glycols ofany desired nominal molecular weight and advantageously having arelatively narrow molecular weight distribution.

If, by way of further example, the activator is the monoethyl ether ofethylene glycol (MEEG) and the derivative is directly alkoxylated withethylene oxide, the product will be a mixture of ethoxylates of MEEGwhose composition will be determined by the molar ratio of ethyleneoxide to MEEG.

As used herein, the term "excess activator" means that amount ofactivator which is not chemically or physically bound to calcium andthus can be removed by simple physical means. The technique employed forthis operation is not critical. Vacuum stripping is recommended for itssimplicity and efficiency, but evaporation and other known proceduresmay also be used.

The derivative will be obtained as a finely divided, particulate solid,in slurry form, which can be readily separated from the reaction mixtureby filtration, decantation, or similar procedures. The product soobtained is catalytically active in alkoxylation reactions, whether ornot acid modified.

The preparation of the supported calcium catalysts of this inventionrequires the reaction of the catalyst precursor, e.g., aryloxy orarylthio-containing supported residues, with the calcium derivative.This particular step, referred to as the "calcium loading" or "metalloading" step, converts the aryloxy or arylthio-containing supportedresidue into a mixed aryl-alkyl calcium alcoholate wherein the arylportion of the mixed alcoholate binds the calcium to the organicpolymeric support and the alkyl portion of the mixed alcoholate suppliesthe catalytic activity to the composition. As pointed out above, thisactive end of the mixed alcoholate may be further modified through apartial modification with a multivalent oxyacid such as sulfuric acid,phosphoric acid and the like, or a metal salt of the multivalent oxyacidsuch as aluminum sulfate, zinc sulfate and the like.

Calcium loading of the functionalized resins, like the synthesis of thecatalyst precursor, can be accomplished by a variety of methods known inthe art. A preferred procedure which may be used to accomplish calciumloading utilizes technology described in U.S. patent application Ser.No. 621,991, filed June 22, 1984. This method involves treatment ofcalcium oxide or calcium hydroxide with an activator to form acalcium-containing composition which subsequently can be reacted with acatalyst precursor, e.g, the aryloxy or arylthio containing supportedprecursor, to produce a catalytically active, supported calciumcomposition of this invention which can alternatively:

1. Be used as such for alkoxylating the alcohol employed as activatorfor the CaO or Ca(OH)₂ ;

2. Be alcohol-exchanged prior to use for alkoxylating the alcohol usedin the exchange reaction; or

3. Be partially modified with a multivalent oxyacid or metal saltthereof prior to use in either alternative #1 or #2 above.

Irrespective of the alternative selected, the heterogeneous calciumcatalyst should, prior to its use, be freed of residual activator orexchanger alcohol by treatment, for example, with some inert (nonactive-hydrogen-containing) solvent followed by removal of the inertsolvent. While not intending in any way to limit the scope of thisinvention to certain recovery or purification procedures, it ispreferred to use ethylene glycol as activator in the preparationsbecause it permits the removal by extraction of unbound or free calciumfrom the catalyst prior to use. In a particularly preferred method ofcatalyst preparation, the resin is loaded by reaction with CaO inethylene glycol medium, freed of unbound alkalinity by extraction(multiple batch or continuous) with ethylene glycol, freed of excessethylene glycol by extraction with ethylene glycol dimethylether orazeotropic distillation with toluene, and dried to remove the residualinert solvent. If this catalyst is to be alcohol-exchanged, then asimilar extraction and drying procedure should be used after exchange toremove excess exchanger alcohol. If a modification step is included inthe preparation, it is preferred that extraction and drying stepsappropriate to the specific catalyst in question be included in thetotal preparative scheme. It is always preferred that the final form ofthe catalyst be one wherein its --X₂ R₃ group be derived from thealcohol which is to be alkoxylated. This prevents productioncontamination via unwanted exchange reactions which can occur duringalkoxylation.

It is a particularly desirable feature of this invention that thecatalyst can be used to provide alkoxylate surfactants having a uniquelynarrow molecular weight distribution, low pour point, and low level ofunreacted starter component. In this usage, the catalyst is contactedwith the starter component, e.g., alcohol under conditions at whichreaction will occur, to perform an alcohol exchange (which can also bereferred to as an alkoxide exchange) reaction. A portion of the starteralcohol thus is present as an alcoholate of calcium, which alcoholate isitself an active species for the alkoxylation reaction. This reactionmixture is then reacted with one or more alkylene oxides, e.g., alkyleneoxides such as ethylene oxide, according to known procedures to producethe desired surfactant.

Referring now to the structural formula given above for the activator, Xand Y are preferably more than one carbon removed from each other, e.g.,in the beta position relative to each other, and are preferably oxygen,as in ethylene glycol, or oxygen and nitrogen, as in monoethanolamine;however, X and Y can also be sulfur or phosphorous. Exemplary of otheruseful compounds are ethylenediamine, N-methylethanolamine,tetrahydrofurfuryl alcohol, 2-mercaptoethanol, 1,2-propylene glycol,2-methylthioethanol, 2-ethoxyethanol, diethylene glycol, 1,3-propanedioland 1,4-butanediol.

Z and Z' are the same or different radicals, optionally substituted, andoften at least one of Z and Z' is selected from the group consisting ofhydrogen, lower linear or branched alkyl of one to four carbon atoms,alkylene from two or about six carbon atoms, phenyl or loweralkyl-substituted phenyl, cycloalkyl of three to about six carbon atomsand alkylene or hetero-atom substituted alkylene rings.

In the activator, Q may comprise a carbon chain of up to six carbonsbetween X and Y. A two- to four-carbon chain is preferred, however,because the activating capacity of X and Y is maximized at such chainlengths. Of these, a two carbon chain length is especially preferred. Inhighly preferred embodiments, Q will be a two-carbon chain and thestructural formula will be as follows: ##STR2## wherein Z, Z', X, Y, aand b are as defined hereinabove and R₆, R₇, R₈, and R₉ are preferablyhydrogen, but may also be lower alkyl or alkylene groups of one to fourcarbon atoms, optionally substituted, or such other radicals as do notinterfere with the usefulness of the activator for its intended purpose.

Also, Q may be cyclic, preferably cycloalkyl of six or fewer carbons,optionally substituted, as can be represented by the formula: ##STR3##Compounds coming within this description would include4-methoxycyclohexane 1,2-diol; 2-aminocyclopentanol; and2-methoxycyclopentanol.

Similarly, either X or Y or both of them could be part of a ringstructure with a carbon atom adjacent to either of them, as illustratedby the formula: ##STR4## Some compounds illustrating such configurationswould include tetrahydrofurfuryl alcohol; furfuryl alcohol;2-hydroxyethyl aziridine; 1-(N methyl-2-pyrrolidinyl) ethanol; and2-aminomethylpyrrolidine.

Moreover, X and Y can themselves be part of the same ring structure,including Q, according to the formula: ##STR5## Exemplary of suchcompounds would be piperazine; 4-hydroxymethyl-2,2-dimethyl-1,3dioxolane; 2,6-dimethylmorpholine; and cyclohexanone ethylene ketal.

Numerous other ring structures, whether saturated or unsaturated,substituted or unsubstituted, are also possible and are intended to bewithin the scope of the present invention.

The only perceived limitation on Q and on the overall structure offormula (I) is that the activator must be capable of solubilizing, atleast in part, CaO and/or Ca(OH)₂. The solubilization of the normallyinsoluble CaO and Ca(OH)₂ is considered to be the threshold step whichpermits these heretofore inoperable materials to be successfullyutilized. Without intending to be bound to any particular theory, thissolubilization is believed to be accomplished through theelectron-withdrawing effects of hetero-atoms X and Y in relation toadjacent carbon atoms, thereby increasing the acidity of the activatormolecule and also helping it to participate in the formation ofcomplexes with calcium, such as exemplified by the structure: ##STR6##Thus, any structure represented by the formula

    Z.sub.a --X--Q--Y--Z'.sub.b

is satisfactory, provided only that it does not eliminate or neutralizethe electronegativity of the hetero-atoms and thus prevent the activatorfrom performing its intended purpose of solubilizing, at least in part,the CaO and/or Ca(OH)₂.

As lime is solubilized, the alkalinity of the medium increases; thus,the building of alkalinity can be used as a screening technique toidentify potentially useful activators. In this test, one should lookfor approximately one or more grams of alkalinity, calculated as CaO,based on 5 grams of calcium (calculated as CaO) charged, as determinedby titration with 0.01 N HCl in ethanol (alcoholic HCl), as will bedescribed more fully below. It should be noted, however, that aminesinterfere with this test, thus, it cannot be dependably used withamine-containing activator candidates.

In the solubilizing step of the process of this invention, as has beenmentioned above, CaO and/or Ca(OH)₂ are mixed with the activator to formone or more derivative species. The purpose of this treatment is tosolubilize sufficient lime to be catalytically effective in analkoxylation reaction; thus, the lime concentration could be eitherbelow or above its solubility maximum in the activator, provided onlythat sufficient lime is solubilized to be catalytically effective. As ageneral guideline, however, the concentration of lime used in theinitial step should typically be in the range of about 1-2%, based onthe activator. The lime should normally be present somewhat in excess ofits solubility in the activator, but lime concentrations exceeding about30% would rarely be considered desirable.

The temperature for this procedure is not considered critical, and canrange from about 50° C. up to the boiling point of the activator,typically well over 200° C. It is desirable to operate in the range ofabout 90° to 150° C., preferably about 125° to 150° C., and the systemcan be put under either vacuum or pressure to maintain any desiredtemperature while maintaining the activator in the liquid phase.Advantageously, the conditions of temperature and pressure are such thatwater can be vaporized and removed from the reaction medium.

Preferably the catalyst preparation is conducted under a substantiallyinert atmosphere such as a nitrogen atmosphere.

To perform this step of the process, lime is simply added to theactivator in a stirred vessel under sufficient agitation to create aslurry of the lime for a period of time adequate to solubilize at leasta portion of the lime. Normally, this will be accomplished within aperiod of about 1 to 4 hours. The amount of lime which will besolubilized will depend, of course, on the concentration of limepresent, the effectiveness of the activator used, and on thetemperature, time and agitation employed. Ideally, the quantity of limedesired for the subsequent alkoxylation reaction is solubilized. Thesource of the lime for this step includes any commercially-availablegrade of quicklime or slaked lime, since the impurities typicallycontained in such lime do not significantly adversely affect thecatalyst formed by the procedures of this invention.

The resulting lime/activator derivative is then reacted with thecatalyst precursor to produce a catalyst for alkoxylation reactions(although it is preferably modified to enhance the narrowness of thealkoxylation product). This would be the case where, for example,ethylene oxide is to be added to the material used as the activator,e.g., ethylene glycol, to produce poly(oxyethylene)glycols of anydesired molecular weight.

If the catalyst is to be used to produce a surfactant or otheralkoxylation product using a different starter, an exchange can beperformed as described above. For example, in producing a surfactant,the catalyst of formula (i) hereinabove can be added to a stirred vesselcontaining a surfactant range alcohol or mixture of such alcohols,typically C₁₂ -C₁₄ alcohols. The concentration of derivative used canvary over a very broad range, but ideally would be approximately thatdesired for the subsequent alkoxylation reaction. The temperature duringthe exchange reaction may be any temperature at which the reaction willoccur, but, preferably, will be in the range of about 200°-250° C., andpressure may be adjusted to achieve these temperatures. If the exchangeprocedure is followed, the activator chosen should have a boiling pointof less than about 200° C. to permit it to be readily stripped from thedetergent alcohol, most of which boil in the 250° C. range or higher.The resulting alcohol-exchanged product is suitable for use directly asa catalyst in alkoxylation reactions to produce surfactants started withthe exchanged alcohol or alcohols although it is preferably acidmodified to enhance the narrowness of the alkoxylation product.

The catalyst produced by the above-described process is often in theform of a stable slurry of finely divided (e.g., about 5 microns)particles, strongly basic (pH about 11-12), and containing excess CaO.

Although not required for alkoxylation reaction, it is highly preferredthat the catalyst of formula (i) hereinabove, or the alcohol-exchangedproduct thereof, be partially neutralized with acid prior to use ascatalyst for alkoxylation if narrower distribution of alkoxylateproducts is desired. While the precise chemical nature of this procedureis not fully understood, it does result in a demonstrable improvement tothe overall process in that the molecular weight distribution isnarrowed still further. In addition, modified catalysts tend to requiredlittle or no induction period in the alkoxylation reaction, and alsoincrease the reaction rate over that of their unmodified counterparts.In contrast, addition of acid to conventional catalysts, such aspotassium hydroxide, slows the alkoxylation rate while producing nobeneficial effect on the product distribution.

Advantageous results can be obtained if the catalyst is used in its"crude" form, i.e., without separation from its reaction mixture orpurification. Nevertheless, if desired, the heterogeneous catalyst,whether modified or not, can be separated from its reaction mixture,purified, dried and stored. Such may be accomplished in astraightforward manner, as by stripping off the excess activator orother organic material containing active hydrogen, filtering theresulting slurry, reslurrying the wet solids with a solvent (e.g.,tetrahydrofuran) and refiltering, and drying, preferably under vacuum.The solids thus obtained will be catalytically active, but, frequently,they are substantially less active than the catalyst in its "crude"form. Reaction rate notwithstanding, however, the desired narrowmolecular weight distribution and other benefits can still be obtained.

It is a highly desirable, and quite unexpected, benefit of this aspectof the invention that the overall process embodied in the variousprocedures described above for making catalysts from lime is remarkably"forgiving" of process variations. Thus, considerable flexibility existsas to the point modifier is added and, within reasonable limits, howmuch modifier is used. Similarly, the unreacted activator may be removedwholly or partially prior to, e.g., an exchange reaction, if used, or itmay be left present during the exchange reaction. Moreover, the catalystmay be re-used indefinitely, used and stored in its "crude" form, orpurified and dried, with any loss in reaction rate made up by increasingtemperature.

The procedures involved in carrying out the process of this inventionare illustrated by the following description directed toward themanufacture of nonionic surfactants.

The manner in which the process of this invention is practiced can beillustrated by the following generalized procedure for preparing aslurry of calcium alkoxylation catalyst intended for use in themanufacture of "peaked" (narrow molecular weight distribution) linearalcohol ethoxylates (nonionic surfactants).

As applied to the specific case of the production of nonionicsurfactants, the process of this invention is characterized by aconsiderable degree of operational latitude. This is particularly truein the preferred version of the process wherein the modified form of thecatalyst is produced. From the standpoint of the chemistry which takesplace, there are four distinct steps in the preparation of theunmodified catalysts and five distinct steps in the preparation of themodified catalysts. Steps 1, 2, 3 and 4, which are common to thepreparation of both catalyst types, involve the following reactions:

Step 1--Reaction of an organic polymer which has a crosslinked,microporous, macroporous or physically expanded structure with acarbocyclic or heterocyclic compound to produce a catalyst precursor.

Step 2--Reaction of lime (or mixtures of major quantities of lime withminor quantities of other alkaline earth bases) with a suitableactivator.

Step 3--Reaction of the catalyst precursor formed in step 1 with theproduct formed in step 2 above.

Step 4--Reaction of the product formed in step 3 above with a detergentrange alcohol to effect exchange of the activator-derived organicradicals for detergent-range alcohol-derived organic radicals.

During or following the exchange reactions of step 4 the activator,which preferably is substantially more volatile than the detergent-rangealcohol, is removed from the system by distillation. At the conclusionof this operation, the unmodified version of the catalyst is obtained inthe form of an activator-free slurry in the detergent-range alcohol.

In the preparation of the unmodified form of the calcium catalyst, steps2 and 4, above, may be combined into one operation wherein the lime isreacted with a mixture of activator and detergent range alcohol. Incases where especially effective activators are being used (e.g.,ethylene glycol, 1,2-propylene glycol, ethylene glycol monoethylether,etc.), this alternative procedure of combining the activator with thedetergent-range alcohol is frequently preferred because it tends tominimize color build-up in the catalyst slurry. From the standpoint ofthe final product characteristics, both procedures are equallyacceptable. Modified processes wherein the activator is fed into aslurry of the detergent-range alcohol and the calcium base or thedetergent-range alcohol is fed into a slurry (or, in some cases, asolution) of the calcium base in the activator are also operationallyviable, although their use offers no perceived advantage over the batchcharging version.

The preparation of the modified catalyst involves a fifth majorprocessing operation which, like that of steps 1, 2, 3 and 4, is adistinct step in terms of the chemistry which takes place.

Step 5--Treatment of the slurry of unmodified catalyst indetergent-range alcohol with a deficiency of some appropriate modifiersuch as polyvalent oxyacid (e.g., H₂ SO₄, H₃ PO₄, H₂ MoO₄, etc.).

This step provides a highly-active, modified calcium catalyst in theform of a slurry in the detergent-range alcohol. The product slurry isnormally subjected to an in vacuo drying operation before it is employedin an ethoxylation reaction to manufacture a nonionic surfactant. Themodifier charge can be based either upon the initial lime charge or,more desirably where possible, upon an "active catalyst" value which isobtained by titrating a sample of the lime/activator reaction mixturefor alkalinity content using 0.01 N alcoholic HCl in the presence ofbromothymol blue indicator. When an inorganic oxyacid is employed, it isconvenient to use the above procedure. A particularly convenientprocedure is to follow the course of the lime/activator reaction bytitration and to base the acid modifier charge upon the alkalinity valueobtained when a constant level of alkalinity has been reached. Anespecially convenient and effective procedure, for example, is to addthe acid modifier at a level of about 50% of this "constant" alkalinityvalue. Monitoring of the lime/activator reaction by titration andultimately determining the acid modifier charge based upon thisanalysis, although frequently a preferred procedure, cannot be used withamino-functional activators because the amine functionality interfereswith the alkalinity analysis. In such instances, the preferred procedureis to base the acid modifier charge on the alkalinity value obtained bytitrating the activator-free (stripped) slurry of catalyst in detergentalcohol.

Because of the fact that this process offers such wide operationallatitude, there is no single procedure which can be said to representthe general procedure. This consideration notwithstanding, one procedurewhich will suffice to illustrate the process is as follows:

A catalyst precursor is prepared via the Williamson etherificationreaction employing a 200-400 mesh Merrifield® Resin (2% crosslinkedpolystyrene chloromethylated to a level of 5 milliequivalents/gram) asthe support reactant and hydroquinone as the phenolic reactant.Alternatively, the catalyst precursor is prepared by Friedel Craftsalkylation of monomethylhydroquinone with a 200-400 mesh Merrifield®Resin of the type described above.

Lime (as commercially supplied or calcined 6 hours at 600° C.) and2-ethoxyethanol (available from Union Carbide) are then charged to asuitably-sized, agitated vessel equipped with a reflux condenser,thermocouple, 10-tray distillation column, and inert gas purge inlet.The reactants are charged in weight ratios ranging from 60 to 80 partsof 2-ethoxyethanol to one part of lime. The charge is heated under anitrogen purge for a period of 2 to 6 hours at the reflux temperature(about 135° C.) while refluxing solvent is removed overhead continuouslyor intermittently- at a make rate sufficiently slow such that during theentire reaction period only about 10 to 15% of the original solventcharge is removed overhead. The purpose of this operation is to removefrom the system water which was either introduced with the reactants orproduced by chemical reaction. During the reflux period, the reactionmixture is sampled at periodic intervals to monitor the buildup of"alkalinity" which is indicative of the formation of catalyticallyactive materials. The analytical method used for this purpose is atitration with 0.01 N HCl in 2-ethoxyethanol using bromothymol blueindicator. When similar "alkalinity" levels are obtained from twosuccessive titrations, the lime/activator reaction step is considered tobe finished. The usual timed period to reach this point is about 4hours.

The catalyst precursor is then reacted with the lime/activator productunder conventional reaction conditions to afford the alkoxylationcatalyst such as illustrated in the examples hereinafter.

At this point the reaction mixture is diluted with the detergent rangealcohol to be ethoxylated; typically the quantity of alcohol added isabout 100 grams/gram of lime (calculated as CaO) used in the initialreaction. The resulting mixture is cooled to about 75° C. and treated,under agitation, with sufficient modifier, preferably sulfuric acid, toneutralize about 50% (on an equivalents basis) of the alkalinityindicated to be present by the final titration performed on thelime/activator reaction mixture.

The temperature is then increased to permit removal of the activatorfrom the reaction mixture by distillation at atmospheric pressure.Distillation at atmospheric pressure is continued until the kettletemperature reaches about 175 to 180° C. At this point the pressure onthe system is reduced to about 180 mm Hg and stripping of the activatoris continued until the kettle reaches a temperature of about 215° to225° C. and both the kettle product and the distillate are free ofactivator as indicated by gas chromatographic (GC) analysis (e.g., lessthan 1000 ppm by weight and often less than 100 ppm by weight).

The thus-obtained activator-free slurry of catalyst in detergent alcoholcan either be used directly as a charge to the ethoxylation reactor or,optionally, diluted with sufficient, dry detergent range alcohol toafford any desired catalyst concentration in the slurry. A final"alkalinity" value on this slurry may, if desired, be obtained by thesame titration procedure described hereinabove.

The above procedure represents but one of many equally viable versionsof this process. The runs summarized in the examples hereinafterillustrate the use of several, but by no means all, of the versionswhich are possible through different combinations of the optionsavailable in the various process steps.

The heterogeneous catalytic reactions of this invention can be effected,for example, by conventional methods such as (1) batch processes; (2)continuous fixed-bed processes; and (3) continuous fluidized reactorprocesses. In a batch reactor, the catalyst is kept suspended in thereactant by shaking or stirring. In a fluidized reactor, the catalyst isat a particular original level. As the velocity of the reactant streamis increased, the catalyst bed expands upward to a second level, and ata critical velocity it enters into violent turbulence. The fluidizedreactor is particularly useful for removing or supplying the heatnecessary to maintain a fixed catalyst temperature. The fluidizedreactor can usually be employed only on a rather large scale since goodfluidization requires a reactor larger than about 1.5 inches indiameter.

The processes of this invention broadly involve the liquid or gaseoususe of heterogeneous calcium-containing catalysts for the alkoxylationof active-hydrogen compounds, preferably hydroxyl-containing compounds,such as, primary or secondary alcohols, diols or triols. Mixtures ofactive-hydrogen compounds can be used.

Alkoxylation product mixtures prepared by the processes of thisinvention comprise alkoxylation species that can be represented by theformula

    R.sub.10 [(CHR.sub.11 --CHR.sub.12 O).sub.r H].sub.s

wherein R₁₀ is an organic residue of an organic compound having at leastone active hydrogen, s is an integer of at least 1 up to the number ofactive hydrogens contained by the organic compound, R₁₁ and R₁₂ may bethe same or different and can be hydrogen and alkyl (including hydroxy-and halo-substituted alkyl) of, for example, 1 to 28 carbons, and r isan integer of at least 1, say, 1 to about 50.

Organic compounds having active hydrogens include alcohols (mono-, di-and polyhydric alcohols), phenols, carboxylic acids (mono , di- andpolyacids), and amines (primary and secondary). Frequently, the organiccompounds contain 1 carbon to about 100 or 150 carbons (in the case ofpolyol polymers) and can contain aliphatic and/or aromatic structures.Most often, the organic compounds are selected from the group of mono-,di- and trihydric alcohols having 1 to about 30 carbon atoms.

Particularly preferred alcohols are primary and secondary monohydricalcohols which are straight or branched chain such as methanol, ethanol,propanol, pentanol, hexanol, heptanol, octanol, nonanol, decanol,undecanol, dodecanol, tridecanol, tetradecanol, pentadecanol,hexadecanol, octadecanol, isopropyl alcohol, 2-ethylhexanol,sec-butanol, isobutanol, 2-pentanol, 3-pentanol and isodecanol.Particularly suitable alcohols are linear and branched primary alcohols(including mixtures) such as produced by the "Oxo" reaction of C₃ to C₂₀olefins. The alcohols may also be cycloaliphatic such as cyclopentanol,cyclohexanol, cycloheptanol, cyclooctanol, as well as aromaticsubstituted aliphatic alcohols such as benzyl alcohol, phenylethylalcohol, and phenylpropyl alcohol. Other aliphatic structures include2-methoxyethanol and the like.

Phenols include alkylphenyls of up to 30 carbons such as p-methylphenol,p-ethylphenol, p-butylphenol, p-heptylphenol, p-nonylphenol,dinonylphenol and p decylphenol. The aromatic radicals may contain othersubstituents such as halide atoms.

Alcohols (polyols) having 2 or more hydroxyl groups, e.g., about two tosix hydroxyl groups and have 2 to 30 carbons, include glycols such asethylene glycol, propylene glycol, butylene glycol, pentylene glycol,hexylene glycol, neopentylene glycol, decylene glycol, diethyleneglycol, triethylene glycol and dipropylene glycol. Other polyols includeglycerine, 1,3-propanediol, pentaerythritol, galactitol, sorbitol,mannitol, erythritol, trimethylolethane and trimethylolpropane.

The alkylene oxides which provide the oxyalkylene units in theethoxylated products include alkylene oxides such as ethylene oxide,propylene oxide, 1,2-butylene oxide, 2,3-butylene oxide, 1,2- and2,3-pentylene oxide, cyclohexylene oxide, 1,2-hexylene oxide,1,2-octylene oxide, and 1,2-decylene oxide; epoxidized fatty alcoholssuch as epoxidized soybean fatty alcohols and epoxidized linseed fattyalcohols; aromatic epoxides such as styrene oxide and 2-methylstyreneoxide; and hydroxy- and halogen-substituted alkylene oxides such aslycidol, epichlorhydrin and epibromhydrin. The preferred alkylene oxidesare ethylene oxide and propylene oxide.

The selection of the organic residue and the oxyalkylene moieties isbased on the particular application of the resulting alkoxylationproduct. Advantageously, narrow distributions can be obtained using awide variety of compounds having active hydrogens, especially monohydricalcohols, which provide desirable surfactants. Because of the narrowdistribution of the alkoxylation product mixture, especially attractivealkoxylation products are surfactants in which certain hydrophilic andlipophilic balances are sought. Hence, the organic compound oftencomprises a monohydric alcohol of about 8 to 20 carbons and the alkyleneoxide comprises ethylene oxide.

While the processes described herein are capable of selectivelyproviding narrow distributions of alkoxylates with the most prevalenthaving as low as one mole of oxyalkylene per mole of active hydrogensite, a particular advantage exists in the ability to provide a narrowdistribution at higher levels of alkoxylation, e.g., wherein the mostprevalent specie has at least 4 oxyalylene units. For some surfactantapplications, the most prevalent alkoxylation specie has 6, 7, 8, 9, 10,11 or 12 oxyalkylene units per active hydrogen site. For many surfactantapplications, it has been found that a relatively few species providethe desired activity, i.e., a range of plus or minus two oxyalkyleneunits. Hence, the compositions of this invention are particularlyattractive in that the range of alkoxylation is narrow, but not sonarrow that a range of activity is lost.

Moreover, the relatively symmetrical distribution of alkoxylate speciesthat can be provided by this invention enhances that balance whileproviding a mixture that exhibits desirable physical properties such ascloud point, freeze point, viscosity, pour point and the like. For manyalkoxylation mixtures of this invention, the species falling within therange of n plus or minus two comprise at least about 75, say, about 80to 95, sometimes 85 to 95, weight percent of the composition.Importantly, the compositions can be provided such that no singlealkoxylation product is in an amount of greater than 50 weight percentof the composition, and, most often, the most prevalent specie is in anamount of 20 to about 30 weight percent, e.g., about 22 to 28, weightpercent, to enhance the balance of the composition.

Another class of alkoxylation product mixtures are thepoly(oxyethylene)glycols. For instance, triethylene glycol andtetraethylene glycol find application in gas dehydration, solventextraction and in the manufacture of other chemicals and compositions.These glycols can be prepared by the ethoxylation of ethylene glycol anddiethylene glycol. Advantageous processes of this invention enableethoxylate product compositions containing at least about 80, say, about80 to 95, weight percent of triethylene glycol and tetraethylene glycol.

Among the most commercially important alkoxylation products are thosewhich utilize water or an alcohol (monols, glyols, polyols, etc.) asstarter (initiator) and ethylene oxide, propylene oxide, or an ethyleneoxide/propylene oxide mixture as the 1,2-alkylene oxide monomer. Suchalcohol ethoxylates encompass a myriad of structures, compositions andmolecular weights intended for service in a diversity of applicationsranging from heavy duty industrial end uses such as solvents andfunctional fluids to ultra-sophisticated, consumer-oriented end usessuch as in pharmaceutical, personal care and household goods. Thesupported catalysts of the instant invention find utility in themanufacture of a broad range of alkoxylation products, but areparticularly useful in the manufacture of alkoxylates designed forservice in sophisticated, consumer-oriented end use areas of applicationwhere product quality demands are stringent. Among the many types ofalkoxylates which are used in such applications, two of the mostprominent are the poly(oxyethylene)glycols and the fatty alcoholethoxylates. The poly(oxyethylene)glycols, known under such tradenamesas CARBOWAX®, POLYGLYCOL E®, PLURACOL E®, etc., are manufactured byethoxylation of ethylene glycol or one of its homologues; they areproduced over a molecular weight range of about 200 to about 8,000. Thefatty alcohol ethoxylates, known under such non-ionic surfactanttradenames as NEODOL®, ALFONIC®, TERGITOL®, etc., are manufactured byethoxylation of linear or branched C₁₀ -C₁₆ saturated alcohols; they areproduced over a molecular weight range of about 300 to about 800. It isin the production of these and other performance type, premium qualityethoxylates that the supported catalysts of the instant invention offermaximum advantages relative to the usual homogeneous ethoxylationcatalysts (NaOH, KOH, etc.) which must be removed ultimately from thefinished product.

The alkoxylation product mixtures of this invention are characterized byhaving a negligible amount of catalyst residues. For purposes of thisinvention, a negligible amount of catalyst residues is an amountsufficient to ensure shelf stability and market acceptability of thealkoxylation product; a catalyst neutralization/catalyst salt removalstep is not required. Preferably, the amount of catalyst residues in thealkoxylation products of this invention is less than 0.01milliequivalents per gram of product. Stated another way, the amount ofcatalyst residues in the alkoxylation product mixtures of this inventionis such that a catalyst neutralization/catalyst salt removal step is notrequired in the processes for preparation thereof.

Conventional alkoxylation products typically contain catalyst residueswhich must be neutralized, at the very least, or more generally, bothneutralized and removed to ensure shelf stability and marketacceptability of the alkoxylate product. Neutralization/removal of suchcatalyst residues is a time-consuming operation which adds significantlyto the cost of the finished alkoxylate product. Some of the proceduresused commercially are the following:

1. Neutralization without Salts Removal--in this case, neutralization isconducted with a species, usually an acid such as acetic acid, whichaffords a salt that is soluble in the ethoxylate product.

2. Neutralization with Salts Removal--similar to above, but conductedwith a species which affords an insoluble salt removable from theproduct by filtration or centrifugation; phosphoric acid is frequentlyused in this procedure.

3. Neutralization with Diatomaceous Earths--in this case, the ethoxylateis neutralized with a diatomaceous earth such as Magnesol®, e.g., andthe salts are removed along with the excess diatomaceous earth byfiltration or centrifugation.

4. Neutralization by Ion-Exchanging--in this case, the product isdiluted with a solvent and passed through a bed containing ion-exchangeresin(s); the effluent from the bed is then subjected to an evaporativedistillation to remove the diluent; the quality of ion-exchangedproducts is very high; however, both capital and operating costs of thisprocess technique are high.

The utility of the supported alkoxylation catalysts of this inventionderives from their capability to afford quality products directly, e.g.,without post-treatments such as neutralization/removal. When utilized ina batch slurry reaction mode, the supported catalyst is separated fromthe reaction product by some simple procedure such as filtration,centrifugation, decantation, etc. In the fixed bed reaction mode, noseparation whatever of supported catalyst from product is required,although a "polishing" filtration of the product may be desirable toremove spurious foreign matter and/or fine particulates which may arisethrough mechanical attrition of the bed packing. In batch reaction modeoperation, separation of the supported catalyst from the alkoxylateproduct is preferably accomplished by a procedure which minimizespossible exposure of the dry or largely dry catalyst to the atmosphere.This is so..because moisture and/or carbon dioxide can be detrimental tothe activity/life of the supported catalyst. Thus, for example,procedures such as centrifugation, decantation, etc., are generallypreferred over filtration, particularly in case where productcross-contamination possibilities do not exist, as in cases wherein thesame product is made from one batch to the next. In cases wherefiltration is necessary, exposure of the final filter cake (in largelydry form at this point) to atmospheric gases should be minimized as muchas possible.

Elimination of a neutralization operation through the use of supportedcatalysts of this invention not only improves process economics, butalso enhances product quality. Quality problems such as color, odor,clarity, residual metal ions, and storage stability, etc., typicallyhave their origins in the catalyst neutralization/catalyst salts removaloperations. It is significant, therefore, that product qualityenhancements accrue from the use of the supported catalysts of thisinvention. The use of supported catalysts will likely gain increasedimportance because of the ever-increasing demands of emergingtechnologies for higher purity ("cleaner") chemical intermediates and ofenvironmental regulatory agencies for less-polluting chemicalmanufacturing operations.

EXAMPLES

This invention is further illustrated by the following examples, whichin no way are intended to limit the applicability or scope of theinvention.

EXAMPLE 1 Part A. Preparation of Catalyst Precursor

To a stirred flask equipped with a reflux condenser and Dean-Stark trapwas charged 10.11 grams of hydroquinone, 6.59 grams of potassiumhydroxide (85% KOH pellets), 37.4 grams of water and 200 grams oftoluene. This mixture was heated at reflux while water was removed asthe bottom layer of toluene/water azeotrope. When water removal wascomplete, the solid suspension was filtered and the solid recovered wascharged back to the same reaction flask along with 20 grams of 200-400mesh Merrifield Resin (2% crosslinked polystyrene chlormethylated to alevel of 5 milliequivalents/gram) and 200 grams of N,Ndimethylformamide. The mixture was heated overnight at reflux, cooled,and filtered. The wet solids recovered (56.1 grams) were slurried in 300grams of water (to dissolve by-product potassium chloride) andrefiltered. The recovered solids were slurried again in 250 grams ofethylene glycol dimethylether (Glyme®), refiltered, and dried in vacuoto give 24.0 grams of catalyst precursor.

Part B. Preparation of Calcium Catalysts

To a stirred reaction flask equipped with distillation head and vacuumcapability was charged 5.0 grams of calcium oxide and 300 grams ofethylene glycol. The system was refluxed at 155° C./190 mm Hg pressurefor 43/4 hours, during which time 26.5 grams of ethylene glycol wasremoved overhead; this overhead ethylene glycol contained 1.34 grams ofwater by analysis. At this point the flask contents were cooled to 85°C. and 22.35 grams of catalyst precursor prepared in Part A were added.Over a period of 13/4 hours 235 grams of ethylene glycol were removedoverhead at 135° C./190 mm Hg pressure. The kettle charge was filtered,the filter cake washed with ethylene glycol dimethylether, and the darkbrown solid dried in vacuo at 10 mm Hg pressure to give 32.0 grams ofcatalyst (hereinafter referred to as Catalyst A). A 2.0 gram quantity ofCatalyst A in this form was used to make fifteen sequential batchpreparations of a poly(oxyethylene)glycol of about 125 molecular weight.These preparations are described in Example 9 hereinafter.

A 10.0 gram portion of Catalyst A was placed in a Soxhlet extractionapparatus and extracted with 300 grams of ethylene glycol for 5 hours at140° C./100 mm Hg pressure. The liquid extractant at the conclusion ofthe treatment contained, by titration, 0.42 grams of calcium oxide. Thesolids recovered were slurried with 200 grams of ethylene glycoldimethylether and dried in vacuo at 10 mm Hg pressure to leave 7.0 gramsof dry catalyst (hereinafter referred to as Catalyst B) as a finepowdery solid. Catalyst B was used in a five run sequential batch seriesof preparations wherein the product was a poly(oxyethylene)glycol ofabout 200 molecular weight. These preparations are described in Example9 hereinafter.

A second portion of Catalyst A was extracted in a Soxhlet extractor asdescribed above. In this experiment, 23.2 grams of Catalyst A wasextracted with 500 grams of ethylene glycol in the Soxhlet apparatus byrefluxing at 155° C./190 mm Hg pressure for 53/4 hours. By titration theliquid extractant removed 1.08 grams of calcium oxide from this charge.The solids remaining were slurried in ethylene glycol dimethylether,recovered by filtration and dried in vacuo at 10 mm Hg pressure to give13.65 grams of powdery catalyst (hereinafter referred to as Catalyst C)which contained 2.58% calcium according to analysis by the ICPE(Inductively Coupled Plasma Emission) technique. The residual chloridecontent in Catalyst C was only 300 ppm. Catalyst C was used to make aseries of ten sequential batch preparations of a poly(oxyethylene)glycolof about 300 molecular weight by ethoxylation of diethylene glycol atabout 140° C. and 20-98 psig pressure. These experiments are describedin Example 9 hereinafter.

EXAMPLE 2 Part A. Preparation of Catalyst Precursor

In the manner similar to that described in

Example 1, Part A, a catalyst precursor was prepared by reacting 20grams of 200-400 mesh Merrifield Resin (2% crosslinked polystyrenechloromethylated to a level of 5 milliequivalents/gram) with themonopotassium salt of hydroquinone (obtained from 10.11 gramshydroquinone and 6.59 grams of 85% potasssium hydroxide by azeotropingoff water of reaction with toluene) overnight in 200 grams of refluxingN,N-dimethylformamide (DMF) and isolating 22.4 grams of a grafted resincatalyst precursor following a recovery procedure which included thesteps of water wash, ethylene glycol dimethylether wash, and vacuumdrying at 140° C., 60 mm Hg pressure.

Part B. Preparation of Calcium Catalysts

The catalyst precursor prepared in Part A was calcium loaded by reacting20.0 grams of this catalyst precursor with the reaction product obtainedby treating 300 grams of ethylene glycol with 5.0 grams of calcium oxidefor four hours at 151° C./180 mm Hg pressure while removing overhead32.5 grams of wet ethylene glycol containing 2.12 grams of water. Afterthe precursor resin had been added to the calcium oxide/ethylene glycolreaction product, the crude catalyst was concentrated by distilling off257 grams of ethylene glycol. The viscous slurry was extracted with 306grams of ethylene glycol at 80-85° C. (1.5 hours) and filtered to give39.6 grams of dark brown solids. After two further extractions in thesame manner followed by a treatment with ethylene glycol dimethyletherand a vacuum drying at 60° C./180 mm Hg pressure, an unmodified catalyst(hereinafter referred to as Catalyst D) was obtained as a mediumbrown-colored solid containing 0.85% calcium by ICPE analysis.

Catalyst D was converted into an acid modified, alkoxide exchangedcatalyst for surfactant preparations by treating 16.6 grams of CatalystD with 150 grams of Alfol 1214 (a C₁₂ /C₁₄ linear alcohol from VistaChemical) and 0.151 grams of concentrated sulfuric acid at 25° C./45 mmHg, distilling off 97.2 grams of Alfol at 162° C./40 mm Hg pressure,slurrying the kettle residue with 200 grams of ethylene glycoldimethylether for 30 minutes, filtering and drying the recovered solidsin vacuo. The dried solid catalyst (hereinafter referred to as CatalystE), exchanged and acid-modified, weighed 16.9 grams and contained byanalysis 0.72% calcium, 0.3% sulfur, and less than 0.07% any othermetallic element. Catalyst E was used to carryout a ten run sequentialbatch preparative series of non-ionic surfactants by ethoxylating Alfol1214 fatty alcohol to approximately a 6.5 mol ethoxylate of cloud pointof about 50° C. This series of experiments is described in Example 10hereinafter.

Catalyst E was also used, after an azeotropic drying with toluene, asthe catalyst for synthesis of some high molecular weightpoly(oxyethylene)glycols by ethoxylation of a PEG-600 starter. Theseexperiments are described in Example 10 hereinafter.

EXAMPLE 3 Part A. Preparation of Catalyst Precursor

To a stirred reaction flask equipped with gas sparger tube, refluxcondenser, and thermometer was charged 20.02 grams of 200-400 meshMerrifield Resin (2% crosslinked polystyrene chloromethylated to a levelof 5 milliequivalents/gram), 131.9 grams of p-methoxyphenol, 850milliliters of 1,2-dichloroethane and 0.12 grams of fused zinc chloride.The mixture was refluxed for 4 days, by which time HCl gas was no longerbeing evolved. The reaction mixture was filtered, the collected solidswashed successively with 0.03 N HCl in dioxane, distilled water andmethanol, and the residual solid dried at 100° C./150 mm Hg pressure.The yield was 25.6 grams of fine orange powder whose ¹³ C solid NMRspectrum was consistent with the expected alkylation product and whichcontained 3.1 milliequivalents/gram of phenolic hydroxyl functionalityappearing at 143-146 ppm with respect to TMS.

Part B. Preparation of Calcium Catalyst

The catalyst precursor prepared in Part A was calcium loaded by reacting20.01 grams of this catalyst precursor with the product formed from thereaction of 5.02 grams of calcium oxide with 300.5 grams of ethyleneglycol in a manner similar to that described in Example 1, Part B. Afterfour extractions with ethylene glycol followed by one extraction withethylene glycol dimethylether and drying at 100° C./150 mm Hg pressure,the unmodified catalyst (hereinafter referred to as Catalyst F) wasobtained in a yield of 21.1 grams. The calcium content by ICPE analysiswas 2.51%.

An acid-modified, fatty alcohol-exchanged calcium catalyst (hereinafterreferred to as Catalyst G) was prepared from Catalyst F by treatingCatalyst F (19.53 grams) with concentrated sulfuric acid (0.400 grams)in the presence of Alfol 1214 fatty alcohol (200.8 grams) at 57° C.followed by removal overhead of 163.6 grams of distillate (ethyleneglycol+Alfol 1214) at a kettle temperature of 167° C./150 mm Hg vacuum.The kettle residue from stripping was filtered, the solid extracted withethylene glycol dimethylether and the ethylene glycol dimethyletherevaporated in vacuo to leave 17.78 grams of Catalyst G as alight-colored particulate solid containing, by analysis, 2.13% calciumand 0.45% sulfur.

The acid-modified, Alfol 1214 exchanged Catalyst G was used to prepare atwenty run batch sequential series of non-ionic surfactants having cloudpoints of about 50° C. at an average ethylene oxide add-on of about 6.5moles per mole of fatty alcohol. This series of preparations isdescribed in Example 11 hereinafter.

EXAMPLE 4

Part A. Preparation of Catalyst Precursor

A catalyst precursor was prepared in a manner similar to that describedin Examples 1 and 2. From 20.0 grams of Merrifield Resin there wasobtained 21.3 grams of a catalyst precursor resin containing the graftedphenolic functionality. Workup of the aqueous wash from the preparationled to the recovery of 5.5 grams of potassium chloride by-product. Thisis 74% of the theory for complete reaction of a Merrifield Resin having5 milliequivalents/gram of chloromethyl functionality.

Part B. Preparation of Calcium Catalyst

The catalyst precursor prepared in Part A was converted to an unmodifiedcalcium catalyst by treating 21.3 grams of the catalyst precursor withthe reaction product from 5.0 grams of calcium oxide and 300 grams ofethylene glycol in a manner similar to that described in Example 1. Theslurry remaining after removal by vacuum distillation of 230 grams ofethylene glycol was slurried twice in ethylene glycol dimethylether, thesolids isolated by filtration, batch-extracted twice with ethyleneglycol, reslurried once again in ethylene glycol dimethylether, filteredoff, and finally dried in vacuo. The yield of unmodified catalyst(hereinafter referred to as Catalyst H) was 19.7 grams; the calciumcontent of this catalyst was 2.95% and residual chloride content was 200ppm. Catalyst H was used to make 5 sequential batch preparations ofPEG-600 by ethoxylation of diethylene glycol starter. Two suchpreparative series were made, each using 4.0 grams of catalystinitially. These preparations are described in Example 12 hereinafter.

EXAMPLE 5 Part A. Description of Catalyst Precursor

Phenolic resin BJO-0930, available from Union Carbide Corporation,Danbury, Conn., is a chemically blown, cross-linked phenolic resin madefrom a caustic- catalyzed phenol/formaldehyde condensate. The expandedspherical beads of resin, known as "microballons", have an average bulkdensity of about 0.08-0.09 grams/cubic centimeter and an average size ofabout 60 microns (150-160 mesh). The resin is reddish-purple in color;its phenolic hydroxyl functionality is 7.8 milliequivalents/gram by ¹³ Csolid NMR and its benyzlic hydroxyl functionality is 3.45milliequivalents/gram by the same technique. As a rough approximation,the resin contains one cross-link per each 10 aromatic rings.

Part B. Preparation of Calcium Catalyst

A mixture of 28.0 grams of calcium oxide and 1500 grams of ethyleneglycol was heated with stirring for seven hours at 131-154° C./100-180mm Hg while 705 grams of ethylene glycol was removed overhead (sevenfractions) to carry-off 9.26 grams of water. At this point, 50 grams ofthe phenolic resin and 1.72 grams of concentrated sulfuric acid wereadded at 55° C. This mixture was heated for 3.75 hours at 154° C./180 mmHg while removing overhead in three fractions another 394 grams ofethylene glycol containing 7.2 grams of water. The charge was thenfiltered, the cake washed with ethylene glycol, and refiltered. The wetsolids thus obtained were batch-extracted 4× with 500-600 gram portionsof ethylene glycol at 70° C. to remove all "free" calcium bases. Theethylene glycol wet catalyst thus obtained (315 grams) was then freed ofethylene glycol by azeotropic distillation with toluene (1000 grams) atatmospheric pressure. When the slurry was free of ethylene glycol, itwas filtered, slurried with fresh toluene at 70° C., refiltered, andfinally dried in vacuo at 100° C./3 mm Hg. The yield of dry catalyst(hereinafter referred to as Catalyst I) was 69.5 grams. The calciumcontent was 6.3% and the sulfur content 160 ppm.

Due to the fact that Catalyst I showed an unexplainably low sulfurcontent, a second acid-modified catalyst was prepared by re-treatingCatalyst I (18.6 grams) with concentrated sulfuric acid (1.2 grams) in228 grams of ethylene glycol at 55° C., stripping off 165.7 grams ofethylene glycol at 154° C./180 mm Hg, finally removing the remainingethylene glycol by azeotropic distillation with toluene, filtering offthe solid (38.2 grams) slurrying the solid in 200 grams of toluene at85° C. for 2 hours, refiltering and finally drying the solid in vacuo at125° C./50 mm Hg pressure. The dried catalyst (hereinafter referred toas Catalyst J) weighed 16.0 grams and analyzed for a calcium content of5.9% and a sulfur content of 0.5%.

Catalyst J was used in a 5-run sequential batch series preparation ofpoly(oxyethylene)glycol of about 300 molecular weight (i.e., PEG-300)conducted in a 1.5 gallon circulated autoclave reactor. This series ofpreparations is described in Example 13 hereinafter.

EXAMPLE 6 Part A. Preparation of Catalyst Precursor

A catalyst precursor was prepared in a manner similar to that describedin Examples 1 and 2; namely, via reaction of 20.0 grams of 20-60 meshMerrifield Resin (3% crosslinked polystyrene chloromethylated to a levelof 4 milliequivalents/gram) with 11.9 grams of the pre-formedmonopotassium salt of hydroquinone in refluxing N,N-dimethylformamide(DMF). The yield of washed and dried grayish colored product was 20.1grams containing 0.8 milliequivalents/gram of phenolic hydroxylfunctionality by NMR analysis. The quantity of by-product potassiumchloride recovered was 3.46 grams.

Part B. Preparation of Calcium Catalysts

An unmodified catalyst was prepared from the catalyst precursor in PartA by calcium loading 19.2 grams of catalyst precursor with the reactionproduct obtained from treatment of 5.0 grams of calcium oxide with 310grams of ethylene glycol at 150° C./180 mm Hg under conditions whereinwater-of-reaction was removed overhead by distilling off about 64 gramsof ethylene glycol during the reaction period of about 4 hours. Thesolid catalyst was recovered by filtration, batch-extracted three timewith 150-200 gram portions of ethylene glycol at 85° C., slurried with200 grams of ethylene glycol dimethylether for 1.5 hours, and finallydried in vacuo at 110° C./5 mm Hg pressure. The dried catalyst(hereinafter referred to as Catalyst K) weighed 18.5 grams and contained1.01% calcium by analysis. An 8.0 gram portion of Catalyst K was used tomake 2 batch preparations of poly(oxyethylene)glycol of about 300molecular weight from ethylene glycol starter in a 1-liter stirredautoclave. These two runs are described in Example 14 hereinafter.

A second 8.0 gram portion of Catalyst K was fatty alcohol-exchanged with220 grams of Alfol 1214 (C₁₂ /C₁₄ linear, primary alcohol from VistaChemical) to prepare an unmodified catalyst for use in surfactantsynthesis. The exchange was carried out by distilling Alfol 1214 offoverhead (carrying the exchanged ethylene glycol along with it) untilthe kettle temperature reached 208° C. at 75 mm Hg pressure. The residue(hereinafter referred to as Catalyst L) used for surfactant preparationconsisted of a slurry of 8.0 grams of exchanged catalyst in 81 grams ofAlfol 1214. This residue was used to prepare the first run in a seriesof four sequential batch surfactant preparations. For runs 2-4 of theseries, the catalyst used was that obtained by filtering in vacuo theprevious run. Thus, the catalyst itself was invariably wet with reactionproduct of the previous batch. These runs are described in Example 14hereinafter.

EXAMPLE 7 Part A. Preparation of Catalyst Precursor

Friedel-Crafts alkylation of p-chlorophenol (137.5 grams) with 20.1grams of 20-60 mesh Merrifield Resin (3% crosslinked polystyrenechloromethylated to a level of 4 milliequivalents/gram) was accomplishedby refluxing for 96 hours in 1,2-dichloroethane (100 milliliters)containing 0.13 grams of fused zinc chloride. The precursor product wasrecovered by successive washes (200 milliliters each) with 0.03 N HCl indioxane, distilled water and methanol followed by drying in vacuo. Thedry catalyst precursor product weighed 25.8 grams and exhibited an NMRspectra consistent with the expected structure.

Part B. Preparation of Calcium Catalyst

An unmodified calcium catalyst was prepared from the catalyst precursorprepared in Part A by calcium loading of the precursor in a mannersimilar to that described previously. Thus the resin (36.8 grams wetwith ethylene glycol) was treated for 4 hours with the reaction productfrom 5.1 grams of calcium oxide and 306.8 grams of ethylene glycol at148° C./140 mm Hg under conditions wherein ethylene glycol wascontinuously fed into the system to replace that removed overhead alongwith water of reaction. After removal of the majority of the remainingethylene glycol by distillation, the kettle residue was filtered and thesolids recovered were subsequently batch-extracted 4 times with 150milliliter portions of ethylene glycol at 70-80° C. Finally, theethylene glycol-wet solids were slurried in ethylene glycoldimethylether, filtered and dried in vacuo to afford the unmodifiedcalcium catalyst (hereinafter referred to as Catalyst M); the weight was24.3 grams and the calcium content was 3.81%. Catalyst M was used forthe preparation of poly(oxyethlene)glycols of about 300 molecular weightfrom diethylene glycol initiator.

A portion of the above unmodified Catalyst M was converted toacid-modified catalyst by treating 11.1 grams of Catalyst M with 0.45grams of concentrated sulfuric acid in 101 grams of ethylene glycol for2 hours at 80-90° C. followed by azeotropically distilling-off theethylene glycol with 151 grams of toluene at reflux. The ethyleneglycol-free resin was recovered by filtration, rinsed with additionaltoluene, and dried in vacuo at room temperature. The yield of modifiedcatalyst hereinafter referred to as Catalyst N) was 10.0 grams of yellowpowdery solid analyzing for 3.99% calcium. This form of the catalyst wasalso used to prepare poly(oxyethylene)glycols of about 300 molecularweight. Both series of poly(oxyethylene)glycol runs are described inExample 15 hereinafter.

EXAMPLE 8 Part A. Preparation of Catalyst Precursor

In a manner similar to that described in Example 3, 132.2 grams ofp-methoxyphenol was Friedel-Crafts alkylated with 20.1 grams of 200-400mesh Merrifield Resin (2% crosslinked polystyrene chloromethylated to alevel of 5 milliequivalents/gram). 1,2-Di-chloroethane (850 milliliters)was used as the reaction solvent and fused zinc chloride (0.1 grams) wasused as catalyst; reaction time was 4 days. The washed and driedprecursor resin weighed 25.6 grams and contained 3.2milliequivalents/gram of phenolic hydroxyl functionality by NMR.

Part B. Preparation of Calcium Catalyst

An unmodified calcium catalyst was prepared from the catalyst precursorprepared in Part A by treating 20.0 grams of the precursor with thereaction product from 5.01 grams of calcium oxide and 301 grams ofethylene glycol. The reaction between the precursor and calciumoxide/ethylene glycol product was carried out at 153° C./180 mm Hgpressure with removal during 31/2 hours of 103 grams of ethylene glycoloverhead. Workup of the catalyst product by filtration followed by fivebatch extractions with ethylene glycol (80-90° C.) and then by a finalwashing with ethylene glycol dimethylether and drying in vacuo affordeda 20.6 grams of reddish-brown solid (hereinafter referred to as CatalystO) containing 1.9% calcium by ICPE analysis.

A 9.0 gram portion of unmodified Catalyst O was converted to anacid-modified catalyst by treatment with 0.21 grams of concentratedsulfuric acid in 100.2 grams of ethylene glycol at 47° C. followed byremoval overhead (129° C. vapor temperature/150 mm Hg pressure) ofethylene glycol (about 157 grams total in seven fractions) containingwater-of-reaction (1.57 grams) and then by filtration, ethylene glycoldimethylether washing and finally drying in vacuo. The acid-modifiedcatalyst (hereinafter referred to as Catalyst P) weighed 8.3 grams andanalyzed for 1.37% calcium and 0.4% sulfur. This catalyst was used foran 8-run sequential batch series of poly(oxyethylene)glycolpreparations. This series is described in Fxample 16 hereinafter.

EXAMPLE 9 Part A. Preparation of Poly(oxyethylene)glycols of about 125Molecular Weight

The catalyst used for this preparation was Catalyst A. A series of 15sequential batch preparations was made with the centrifuged catalystbeing recycled each time to the next batch; the standard charge ofethylene glycol (EG) was 40.0 grams for each batch and the targetquantity of ethylene oxide (EO) to be fed was also 40.0 grams/batch. Thereactor used was a 300 milliliter stirred autoclave (PARR REACTOR) whichwas operated at 140° C. and about 20-110 psig; ethylene oxide was fedincrementally from a pressurized (N₂) stainless steel tank mounted atopa Mettler balance so that the weight of ethylene oxide fed wasdetermined by the weight decrease in the feed tank. Details for thesepreparations and data characterizing the products are given in Table Ibelow. FIG. 5 depicts the average ethoxylate distribution forpoly(oxyethylene)glycols prepared in this example (supported CaO) aswell as unsupported KOH and unsupported CaO.

    TABLE I      RUN NO. IN SERIES 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15       PREPARATIONS REACTANT WEIGHTS, g                Ethylene Glycol 40.0     40.0 40.0 40.0 40.0 40.0 40.0 40.0 40.6 40.0 40.0 40.0 40.0 40.0 40.0     Catalyst.sup.a 2.0 5.2 5.4 6.0 4.4 2.2 3.7 2.5 4.8 3.1 3.1 2.9 2.6 3.1     2.4 Ethylene Oxide.sup.b 40.0 40.4 40.0 40.0 40.0 40.0 40.0 40.0 40.0     40.8 40.0 40.0 40.0 40.0 40.1  (38.5) (31.6) (41.7) (35.7) (37.8) (40.0)     (37.0) (38.8) (38.4) (41.6) (39.9) (45.3) (40.8) (40.7) (39.1) REACTION     TIME, HRS..sup.c 1.7 5.5 10.0 11.0 11.5 12.7 12.7 12.8 13.2 14.2     .sup.˜ 14 .sup.˜ 14 .sup.˜ 13.5 .sup.˜ 13.5     .sup.˜ 13 PRODUCT WEIGHT, g. 80.5 76.8 87.1 81.7 82.2 82.2 80.7     81.3 83.8 84.7 83.0 88.2 83.4 83.8 81.6 MATERIAL BALANCE, % 98.2 89.7     102.0 95.0 97.4 96.8 96.4 98.5 98.1 101.2 99.9 106.4 101.0 100.9 98.9     CHARACTERIZATION Mols EO Added/Mol EG 1.465 1.415 1.24 1.21 1.315 1.24     1.275 1.37 1.34 1.40 1.33 1.53 1.335 1.37 1.385 Hydroxyl Number, 442.8     451 480.7 486.1 467.9 481.6 474.6 458.0 463.6 454.3 466.0 433.5 464.4     458.7 456.1 mg KOH/g Alkalinity, % as 0.037 0.006 0.0004 nil nil nil nil     nil nil nil nil nil nil nil nil CaO.sup.d Molecular Weight 126.7 124.4     116.7 115.4 119.9 116.5 118.2 122.5 121.0 123.5 120.4 129.4 120.8 122.3     123.0 pH, 5% Aqueous Sol'n 10.7 9.0 6.2 5.9 5.8 5.7 5.4 5.3 5.4 5.4 5.7     5.3 5.5 6.1 5.9 Unreacted Ethylene 16.1 16.9 25.5 23.6 25.9 23.9 24.3     22.4 22.9 -- 21.3 18.1 21.5 21.4 20.6 Glycol Content, Wt. %.sup.e     ETHOXYLATE DISTRIBUTION, AREA %.sup.f Ethylene Glycol 18.8 19.0 27.2     27.0 27.3 26.0 25.0 25.0 25.8 23.3 25.5 21.7 24.4 23.5 24.7 Diethylene     Glycol 30.3 34.8 30.8 32.4 35.1 33.1 31.8 31.2 32.5 30.8 31.2 28.9 31.3     30.3 29.4 Triethylene Glycol 28.9 28.8 25.7 24.5 22.6 24.2 24.6 24.3     23.5 24.7 23.8 25.4 24.7 23.9 23.5 Tetraethylene Glycol 16.1 12.8 12.2     11.6 10.6 11.7 12.7 12.5 12.3 13.8 12.8 15.2 13.1 13.8 13.6 Pentaethylene      Glycol 4.8 3.9 3.5 3.7 3.6 4.0 4.6 4.7 4.7 5.6 5.1 6.6 5.0 5.6 5.6     Hexaethylene Glycol 0.9 0.7 0.6 0.8 0.9 1.1 1.3 1.3 1.1 1.8 1.6 2.2 1.5     2.0 2.2     .sup.a Catalyst weight for Run #1 is dry resin; for all runs thereafter,     weight includes liquids absorbed on resin.     .sup.b Ethylene oxide weight is that indicated by balance to have been     removed from feed tank. Value in parentheses is weight calculated by     subtracting ethylene glycol and catalyst charge weight from final product     weight.     .sup.c Reaction times are only approximate for runs 3-15 because the     system ran unattended during final cookout.     .sup.d By titration with 0.01 N alcoholic HCl using bromothymol blue     indicator.     .sup.e By gas chromatography using an ndecanol internal standard with     OV101 column on Regisilderivatized sample.     .sup.f By gas chromatography using an OV101 column on Regisilderivatized     sample.

Part B. Preparation of Poly(oxYethylene)glycols of about 300 MolecularWeight

The catalyst for these preparations was Catalyst C, an extracted, washedand dried version of Catalyst A. Catalyst C was used to make a 10-runsequential batch series of poly(oxyethylene)glycol preparations usingdiethylene glycol (DEG) as initiator and the same equipment and catalystrecovery/recycle procedure as described in Part A above. In this case,standard target charges for each batch were 40.0 grams of diethyleneglycol and 73.2 grams of ethylene oxide. Experimental details for thesepreparations and product characterization data are presented in Table IIbelow. FIG. 3 depicts the average ethoxylate distribution forpoly(oxyethylene)glycols prepared in this example supported CaO) as wellas unsupported KOH and unsupported CaO.

                                      TABLE II                                    __________________________________________________________________________    NO. OF RUNS            10.sup.a                                                                             1        1       1                              CATALYST TYPE          Supp. CaO                                                                            Non-supp. KOH                                                                          Non-supp. CaO                                                                         Non-supp. KOH                                         (Catalyst C)                                           CATALYST CONC., %      0.19   0.23     0.25    --                             ON STARTER                                                                    REACTION TIME, HRS..sup.b                                                                            ˜15.sup.c                                                                      0.53.sup.d                                                                             4.7     --                             PRODUCT CHARACTERIZATION                                                      Mols EO/Mol DEG        4.15   4.595    4.425   4.39                           Hydroxyl No. mg KOH/g  389.4  363.9    372.8   374.2                          Molecular Weight       288.1  307.3    300.9   299.0                          Alkalinity, meg/g      0.001.sup.e                                                                          0.008    0.022   n/a                            Unreacted DEG, wt %    1.63   <0.1     0.34    <0.1                           ETHOXYLATE DISTRIBUTION, AREA %                                               Diethylene Glycol      3.22   ˜0.1                                                                             0.67    <0.1                           Triethylene Glycol     1.33   2.40     0.54    2.81                           Tetraethylene Glycol   9.92   8.51     8.36    10.1                           Pentaethylene Glycol   23.03  14.82    19.13   16.86                          Hexaethylene Glycol    24.89  18.40    24.08   20.05                          Heptaethylene Glycol   18.14  20.27    21.06   20.01                          Octaethylene Glycol    10.34  16.55    14.11   14.85                          Nonaethylene Glycol    5.23   10.67    7.58    8.90                           Decaethylene Glycol    2.49   5.54     3.25    4.32                           Undecaethylene Glycol  1.0    2.24     0.96    1.67                           Dodecaethylene Glycol  0.23   0.60     0.15    0.44                           __________________________________________________________________________     .sup.a Average values for the 10 runs comprising the series unless            otherwise noted.                                                              .sup.b Reaction times are approximate for supported catalyst runs.            .sup.c Approximate average for runs 3- 6, considered "normal" runs becaus     of absence of "free" alkalinity and reactor operational problems.             .sup.d Reaction was strongly exothermic, so that average temperature was      considerably greater than 140° C.                                      .sup.e Reflects residual alkalinity which was removed after first two         passes.                                                                  

Part C. Preparation of pOly(oxyethylene)glycols of about 200 MolecularWeight

The catalyst for these preparations was Catalyst B, another glycolextracted version of Catalyst A. The poly(oxyethylene)glycolpreparations comprised a sequential series of 5-runs wherein ethylenelycol was used as initiator and a 1.5 gallon circulated autoclave asreactor. Ethylene oxide feed to this reactor was motor-valve controlled,the oxide being introduced as necessary to maintain about 60 psigpressure. A standard ethylene glycol initiator charge was about 500grams; this charge requires about 1100 grams of ethylene oxide toadvance the molecular weight to 200. The catalyst charge was 7.0 gramsof a 2.02% calcium containing resin; catalyst was recovered bycentrifugation and recycled without cleanup or supplementation by freshcatalyst. This run series is summarized in Table III below. FIG. 4depicts the average ethoxylate distribution for poly(oxyethylene)glycolsprepared in this example (supported CaO) as well as unsupported KOH andunsupported CaO.

                                      TABLE III                                   __________________________________________________________________________                           RUN NO. IN SERIES.sup.a                                PREPARATION            1    2    3    4    5                                  __________________________________________________________________________    REACTANT WEIGHTS, g.                                                          Ethylene Glycol        500  500  507.5                                                                              460  458                                Catalyst.sup.b         7.0  9.5  7.85 14.0 21.4                               Ethylene Oxide         1114 1116 1137 1056 1068                               REACTION TEMP., °C..sup.c                                                                     139-141                                                                            139-150                                                                            138-150                                                                            138-150                                                                            138-151                            REACTION TIME, HRS..sup.d                                                                            4.0  9.0  46.5.sup.e                                                                         28.3 37.7                               WEIGHT OF PRODUCT, g.  1560 1542 1533 1452 1477                               MATERIAL BALANCE, %    96.2 94.9 92.8 94.9 95.5                               CHARACTERIZATION                                                              Mols EO Added/Mol EG   3.05 3.06 3.075                                                                              3.205                                                                              3.405                              Hydroxyl No., mgKOH/g  571.0                                                                              570.6                                                                              567.8                                                                              552.4                                                                              529.4                              Alkalinity, % as CaO.sup.f                                                                           0.0063                                                                             0.0014                                                                             nil  nil  nil                                Molecular Weight       196.5                                                                              196.6                                                                              197.4                                                                              203.1                                                                              211.9                              pH, 5% Aqueous Sol'n.  6.4  6.0  5.1  5.2  5.2                                Unreacted Ethylene Glycol,.sup.g                                                                     1.58 2.16 2.72 3.36 1.20                               Content, Weight %                                                             ETHOXYLATE DISTRIBUTION, AREA %.sup.h                                         Ethylene               2.31 2.79 4.17 5.62 2.25                               Diethylene Glycol      6.51 6.87 7.78 5.73 6.75                               Triethylene Glycol     21.44                                                                              21.10                                                                              20.80                                                                              20.24                                                                              21.04                              Tetraethylene Glycol   29.25                                                                              28.70                                                                              26.95                                                                              26.29                                                                              25.83                              Pentaethylene Glycol   21.76                                                                              21.72                                                                              21.04                                                                              20.70                                                                              20.41                              Hexaethylene Glycol    11.92                                                                              12.12                                                                              12.04                                                                              12.64                                                                              12.96                              Heptaethylene Glycol   5.05 5.12 5.45 6.11 6.67                               Octaethylene Glycol    1.61 1.51 1.78 2.26 2.86                               Nonaethylene Glycol    0.16 0.08 <0.1 0.40 0.99                               Decaethylene Glycol    --   --   --   --   0.24                               __________________________________________________________________________     .sup.a Runs in this series carried out in a circulated loop reactor.          .sup.b Catalyst weight for run #1 is dry resin; for all runs thereafter,      weight includes liquids absorbed in resin.                                    .sup.c Temperatures of 140° C. were used as necessary to increase      reaction rate.                                                                .sup.d Reaction times are approximate for runs 2-5 made partially under       nonattended conditions.                                                       .sup.e Time is not accurate; mechanical problems caused delays.               .sup.f By titration with .01 N alcoholic HCl using bromothymol blue           indicator.                                                                    .sup.g By gas chromatography using ndecanol internal standard with OV101      column on Regisil derivatized sample.                                         .sup.h By gas chromatography using OV101 column on Regisil derivatized        sample.                                                                  

EXAMPLE 10 Part A. Preparation of Fatty Alcohol Ethoxylates

A series of 10 sequential batch preparations of C₁₂ /C₁₄ primary alcoholethoxylates was made in a 600 milliliter stirred autoclave (a systemsimilar to that in Parts A and B of Example 9). Following each run thecatalyst, i.e., Catalyst E, was recovered by centrifugation and recycledwithout further treatment. Standard charge of C₁₂ /C₁₄ primary alcoholinitiator (mole wt. 202) was 40.0 grams; target ethylene oxide quantitywas 6.5 moles/moles initiator, but usual practice was to introducesufficient ethylene oxide to give an ethoxylate of cloud point of about45-55° C. The run series was started with 8.0 grams of Catalyst E, butthis quantity increased throughout the series as product absorbed on theresin. At the completion of the series of runs, Catalyst E was extracted4× with ethylene glycol dimethylether to remove this absorbed product;the final catalyst weight after this treatment was about 22 grams.Experimental conditions for these runs and product characterization dataare presented in Table IV below.

                                      TABLE IV                                    __________________________________________________________________________                 RUN NO. IN SERIES                                                PREPARATION  1    2    3    4    5    6    7    8    9    10                  __________________________________________________________________________    Reactant Weights, g.                                                          Alfol 1214.sup.a                                                                           40.0 40.0 40.4 40.0 40.0 40.0 40.0 40.0 40.0 40.2                Catalyst.sup.b                                                                             8.0  21.3 28.3 36.2 44.2 44.1 48.3 51.7 53.2 53.5                Ethylene Oxide.sup.c                                                                       57.0 77.5 69.3 73.2 62.0 68.2 70.1 66.0 65.0 66.7                Temperature, °C.                                                                    139-142                                                                            139-141                                                                            140-141                                                                            140  140-142                                                                            139-140                                                                            140-142                                                                            140  138-142                                                                            139-140             Pressure, psig                                                                             10-80                                                                              8-82 10-74                                                                              10-68                                                                              12-80                                                                              11-80                                                                              11-72                                                                              10-78                                                                              12-80                                                                              10-74               Reaction time, hrs..sup.d                                                                  7.25 14.5 .sup.˜ 14                                                                    14.6 12.3 .sup.˜ 12                                                                    15.5 15.2 .sup.˜                                                                       13                  Product Weight, g.                                                                         102.6                                                                              134.7                                                                              138.8                                                                              142.4                                                                              143.0                                                                              149.4                                                                              155.0                                                                              157.0                                                                              155.6                                                                              160.6               Material Balance, %.sup.e                                                                  97.7 97.0 100.6                                                                              95.3 97.8 98.1 97.9 99.6 98.4 100.1               Product Characterization                                                      Appearance, 22° C..sup.k                                                            sl. liq.                                                                           sl. sol                                                                            wax  wax  wax  sl. sol.                                                                           wax  sl. sol.                                                                           wax  wax                 Molecular Weight,                                                                          411.6                                                                              525.1                                                                              527.6                                                                              492.0                                                                              484.6                                                                              481.2                                                                              524.5                                                                              513.9                                                                              501.2                                                                              493.8               (by OH No.)                                                                   Mols EO/Mol Alfol 1214.sup.j                                                               4.77 7.34 7.40 6.59 6.43 6.34 7.33 7.09 6.79 6.64                Alkalinity, % as CaO.sup.f                                                                 0.0093                                                                             nil  nil  nil  nil  nil  nil  nil  nil  nil                 pH, 5% Aqueous Solution                                                                    7.7  6.85 6.9  6.8  6.9  6.8  6.9  6.8  6.9  6.9                 Cloud Point, °C. (1% sol'n.)                                                        <20  55   57   55.5 46   53.5 54   53   48   45                  Unreacted Alcohol, wt. %.sup.g                                                             4.45 1.9  1.3  1.0  1.4  1.0  0.9  1.0  0.95 0.9                 Ether Insolubles, wt. %.sup.h                                                              9.8  7.2  8.0  8.3  7.6  8.1  9.4  8.8  10.8 10.6                Major Component,.sup.i                                                                     5 EO 7 EO 6,7 EO                                                                             6 EO 6 EO 6 EO 6 EO 6 EO 6 EO 5 EO                Area %                                                                        C.sub.12-6 -C.sub.14-7, Area %                                                             28.4 30.9 33.9 35.5 31.7 35.8 33.4 33.6 32.1 31.1                C.sub.12-5 -C.sub.14-8, Area %                                                             52.6 56.2 60.2 62.7 58.4 63.6 60.6 60.3 59.6 58.6                Calcium Content, ppm                                                                       21   15   18   17   14   12.5 12   12   11   11                  Total Metals Content, ppm                                                                  .sup.˜ 34                                                                         .sup.˜ 25                                                                         .sup.˜ 19                                                                         .sup.˜ 18                                                                         .sup.˜             __________________________________________________________________________                                                         17                        .sup.a Alfol 1214 is a Conoco (Vista Chemical) C.sub.12 /C.sub.14 linear      primary alcohol of about 202 molecular weight  water content is 0.04%.        .sup.b Catalyst was Catalyst E, an acidmodified version of hydroquinone       grafted catalyst. The gain in catalyst charge following run #1 represents     material absorbed on resin.                                                   .sup.c Weight of EO indicated to have been fed based upon weight loss in      feed rank.                                                                    .sup.d Reaction times are approximate and do not include overnight            cookdown times.                                                               .sup.e No corrections made for weight losses resulting from sample            removal(s).                                                                   .sup.f By titration with 0.01N alcoholic HCl in CELLOSOLVE using              bromothymol blue indicator.                                                   .sup.g Gas chromatography determination on Regisil ® derivatized          sample using ndecanol as internal standard; SP2100 column.                    .sup.h By extracting 25 grams of product with 250 grams ether at              25° C.                                                                 .sup.i Gas chromatography determination using Regisil ® derivatized       sample; SP2100 column.                                                        .sup.j Theoretical quantity only of ethylene oxide was fed; no attempt wa     made to increase feed to obtain a 50° C. cloud point.                  .sup.k Sl. = slushy; liq. = liquid; sol. = solid.                        

Part B. Preparation of High Molecular Weight Poly(oxyethylene)glycols

Catalyst E used above in Part A for the preparation of C₁₂ C₁₄ primaryalcohol ethoxylates was also used to prepare some high molecular weightpoly(oxyethylene)glycols. The reactor system employed for this work wasthat described in Part A above; namely, a 600 milliliter stirredautoclave equipped with an internal cooling coil. Three runs were madewith poly(oxyethylene)glycol of about 600 molecular weight as initiator;the molecular weights attained in these runs were 2432, 3501 and 4083,respectively. The catalyst for each run was that recovered from theprevious run after isolation by filtration of the solvent-dilutedproduct and drying in vacuo. The initial catalyst charge was 3.5 grams.The reaction products were taken up in solvents out of necessity becausethese poly(oxyethylene)glycols are solids at ordinary temperatures.Conditions for these preparations and product characterization data arepresented in Table V below. The fourth tabulated run, i.e. Run No. 4,represents an unsuccessful attempt to prepare a poly(oxyethylene)glycolof greater than 6000 molecular weight by supported catalysis. In thiscase, the product from Run No. 3 was used as initiator, but themolecular weight could not be further advanced. It is felt that tracesof water in the raw materials/reactor system acted to prevent growth inmolecular weight since ethylene oxide was in fact consumed in thereaction. In any case, Table V does demonstrate that high molecularweight poly(oxyethylene)glycols e.g., up to 4000) can be obtained usingthe supported calcium catalyst of this invention.

                                      TABLE V                                     __________________________________________________________________________                       RUN NO.                                                                       1       2    3    4                                        __________________________________________________________________________    REACTANTS, g                                                                  Catalyst           3.5.sup.a                                                                             13.3.sup.b                                                                         13.5.sup.c                                                                         10.3.sup.d                               PEG-600.sup.e      30.0    20.0 20.62                                                                              --                                       PEG-4083.sup.f     --      --   --   41.71                                    Ethylene Oxide.sup.g                                                                             189.5   199.2                                                                              136.9                                                                              41.85                                    REACTION CONDITIONS                                                           Temperature, °C.                                                                          128-140 129-147                                                                            139-148                                                                            122-148                                  Pressure, psig     11-98   10-98                                                                              10-110                                                                             8-112                                    Time, hours        ˜33                                                                             ˜52                                                                          ˜37                                                                          ˜40                                Prod. Recovery Solvent                                                                           Ethylene glycol                                                                       Acetone                                                                            Acetone                                                                            Acetone                                                     dimethylether/                                                                Acetone                                                    PRODUCT CHARACTERIZATION                                                      Product wt., g.    202.6   204.8                                                                              151.6                                                                              80.5                                     Molecular wt.                                                                 Theoretical        4381    6563 4576 8192                                     Actual             2432    3501 4083 3985                                     pH, 5% solution    4.1     3.8  3.5  3.9                                      Recovered Cat., g. 13.3    13.5 10.4 9.7                                      Viscosity, 50%                                                                solution (25° C.), cks                                                                    94.4    99.8 188.9                                                                              365.2                                    Melting Point, °C.                                                                        56-57   57.5-59                                                                            57.5-59                                                                            59-60                                    __________________________________________________________________________     .sup.a Catalyst was Catalyst E; hydroquinonegrafted, acid modified 200-40     mesh Merrifield Resin which was subjected to azeotropic distillation with     toluene.                                                                      .sup.b Catalyst was recycled from Run No. 1 after recovery from ethylene      glycol dimethylether and acetone media and drying in vacuo to constant        weight.                                                                       .sup.c Catalyst was recycled from Run No. 2 after recovery from acetone       medium and drying in vacuo.                                                   .sup.d Catalyst was recycled from Run No. 3 after recovery from acetone       medium and drying in vacuo.                                                   .sup.e A poly(oxyethylene)glycol which contained 0.19% water and had a        molecular weight of 599 by hydroxyl number method.                            .sup.f This poly(oxyethylene)glycol initiator was the reaction product        from Run No. 3.                                                               .sup.g Weights shown obtained by actual weighing of gross product and         subtracting out weights of initiator and catalyst.                       

EXAMPLE 11 Preparation of Fatty Alcohol Ethoxylates

The catalyst used to prepare this series of C₁₂ /C₁₄ primary alcoholethoxylates was Catalyst G. A series of twenty sequential batchpreparations were carried out, the target products being the same 6.5mol ethylene oxide adducts of C₁₂ /C₁₄ alcohol described in Example 2.The recovered catalyst from each run was extracted with hot toluene,filtered and dried in vacuo before recycling. In this manner, theinitial 8.0 gram catalyst charge increased in weight only to 16.8 ramsover the course of the experiments. The standard C₁₂ /C₁₄ alcoholinitiator charge was 40.0 in these preparations and the target ethyleneoxide feed was 6.5 moles/mole initiator or, more usually, the amountrequired to reach about a 40-50° C. cloud point non-ionic surfactantproduct. The reactor used for these experiments was the 600 milliliterstirred autoclave described previously. Table VI below gives pertinentdata characterizing the product surfactants and experimental conditions.The reaction rate data of Table VI can be put into proper perspective bynoting that the rate for the uncatalyzed reaction of Alfol 1214 withethylene oxide is about 0.003 grams/minute. FIG. 1 depicts the averageethoxylate distribution for fatty alcohol ethoxylates prepared in thisexample (supported CaO/H₂ SO₄) as well as unsupported CaO, unsupportedKOH and unsupported CaO/H₂ SO₄.

    TABLE VI      RUN NO. IN SERIES PRODUCT PREPARATION 1 2 3 4 5 6 7 8 9 10       REACTANT WEIGHTS, g ALFOL 1214 40 40 40 40.2 40 40 40 40.1 40.1 40     CATALYST.sup.a 8.0 38.5 36.2 29.3 25.9 25.65 24.7 24.2 23.9 23.3     ETHYLENE OXIDE 104.5 69.0 70.0 59.7 60.6 59.1 60.4 57.7 57.6 57.3     AGITATOR SPEED, rpm 610 610 610 610 610 610 610 610/490 490 490 TEMPERATU     RE, °C. 140-142 140-142 139-140 140-143 140-143 140-141 140-143     145-147 150-152 155-158 PRESSURE, psig 10-98 10-88 10-92 10-82 10-88     10-67 10-66 10-66 10-62 10-64 FEED MODE.sup.b I/C I I I I/C I/C C C C C     REACTION TIME, HRS..sup.c 12.0 6.0 6.0 7.5 5 5.8 7 5.7 6.25 5.75     REACTION RATE, g/min 0.15 0.19 0.19 0.13 0.20 0.17 0.15 0.17 0.12 0.17     CRUDE NET WEIGHT, g..sup.d 149.4 145 143 132.5 130 125 125.5 120 121     119.9 MATERIAL BALANCE, % 98.0 98.6 97.8 102.6 102.4 99.7 100.3 98.4     99.5 99.4 PRODUCT WEIGHT, g..sup.e 100.6 112.5 108.2 101.1 101.2 97.75     101.0 99.9 98.9 96.5 RECOVERED CATALYST, g.sup.f 38.05 36.2 29.4 25.9     25.65 24.7 24.2 23.9 23.3 23.7 PRODUCT CHARACTERIZATION APPEARANCE,     22° C. SLUSHY WAXY WAXY WAXY WAXY SLUSHY SLUSHY SLUSHY SLUSHY     SLUSHY  SOLID SOLID SOLID SOLID SOLID SOLID SOLID SOLID SOLID SOLID     HYDROXYL NUMBER 111.6 104.8 107.6 108.4 112.1 114.1 115.7 119.5 116.1     116.9 MOLECULAR WT. (by OH No.) 502.5 535.3 521.1 517.6 500.7 491.7     485.0 469.4 483.2 480.1 CLOUD POINT, °C. (1% soln.) 45 47 47 52     50 45.5 47 38 41.5 40 MOLS EO/MOL ALFOL.sup.h 6.83 7.57 7.25 7.17 6.79     6.59 6.43 6.08 6.39 6.32 PH, 5% AQ. SOLN. 6.9 4.7 4.9 6.0 6.2 5.6 5.7     7.0 6.9 7.0 UNREACTED ALCOHOL,.sup.i WT % 0.97 0.76 1.06 0.92 0.88 1.42     1.54 2.53 2.63 2.63 ALKALINITY, % AS CaO.sup.j 0.0008 NIL NIL NIL NIL     NIL NIL NIL NIL NIL ETHER INSOLUBLES, WT %.sup.k 12.6 18.3 26.6 12.0 9.6     6.3 9.1 6.1 5.2 5.6 MAJOR COMPONENT, AREA % E-6 E-6 E-6 E-6 E-6 E-6 E-6     E-6 E-6 E-6 C.sub.12-6 -C.sub.14-7, AREA %.sup.l 39.58 39.99 41.70 43.46     41.89 40.54 40.44 37.08 38.76 37.19 C.sub.12-5 -C.sub.14-8, AREA %.sup.l     69.19 69.86 72.69 74.03 72.12 70.28 70.06 65.18 67.20 65.04 Ca CONTENTS,     ppm.sup.m PRODUCT 135 -- 140 -- 35 -- 16 -- 60 -- BY-PRODUCT -- 525 --     250 -- 437 -- 265 -- 185       RUN NO. IN SERIES PRODUCT PREPARATION 11 12 13 14 15 16 17 18 19     20      REACTANT WEIGHTS, g ALFOL 1214 40 40 40.sup.g 40.sup.g 40.1.sup.g      40.0 40.9 40 40.1 40.0 CATALYST.sup.a 23.7 22.9 22.2 21.3 20.6 18.9     18.1 17.9 17.2 16.8 ETHYLENE OXIDE 57.8 60.2 58.0 64.1 71.5 57.8 58.5     58.1 58.0 58.4 AGITATOR SPEED, rpm 490 389 389 389 389 490 490 490 490     490 TEMPERATURE, °C. 130-132 137-140 139-142 149-152 139-142     140-142 140-142 139-141 140-142 140-142 PRESSURE, psig 10-73 10-70 10-62     10-79 10-46 10-60 10-62 10-62 10-62 10-64 FEED MODE.sup.b C C C C/I C C     C C C C REACTION TIME, HRS..sup.c 8.3 7.75 8.25 9.25 15.0 9.65 10.5 11.0     10.0 14.0 REACTION RATE, g/min 0.12 0.13 0.12 0.12 0.08 0.10 0.09 0.09     0.10 0.07 CRUDE NET WEIGHT, g..sup.d 125.02 122 116.6 123.7 123.6 114.7     117.3 119.3 113.8 120.2 MATERIAL BALANCE, % 102.8 99.1 97.0 98.6 93.5     98.3 99.8 102.3 98.7 104.3 PRODUCT WEIGHT, g..sup.e 99.1 98.6 94.4 101.2     101.6 96.4 97.9 99.5 97.9 100.7 RECOVERED CATALYST, g..sup.f 22.9 22.2     21.3 20.6 18.9 18.1 17.9 17.2 16.8 16.6.sup.f* PRODUCT CHARACTERIZATION     APPEARANCE, 22° C. SLUSHY SLUSHY SLUSHY WAXY SLUSHY SLUSHY SLUSHY     SLUSHY SLUSHY SLUSHY  SOLID SOLID SOLID SOLID SOLID SOLID SOLID SOLID     SOLID SOLID HYDROXYL NUMBER 115.1 116.5 117.4 116.6 118.4 120.9 120.0     113.7 118.9 117.1 MOLECULAR WT. (by OH No.) 487.5 480.9 477.7 481.2     473.7 464.1 467.4 493.5 471.9 479.1 CLOUD POINT, °C. (1% soln.)     47 44 42.5 39 37 38 38.5 48 38.5 51 MOLS EO/MOL ALFOL.sup.h 6.49 6.35     6.27 6.34 6.17 5.96 6.03 6.62 6.13 6.30 PH, 5% AQ. SOLN. 6.8 7.1 6.9 7.2     6.8 6.9 6.7 7.3 6.7 6.9 UNREACTED ALCOHOL,.sup.i WT % 2.38 1.76 2.29     3.48 4.25 3.59 3.39 2.3 2.9 1.8 ALKALINITY, % AS CaO.sup.j NIL NIL NIL     NIL NIL NIL NIL NIL NIL NIL ETHER INSOLUBLES, WT %.sup.k 8.2 8.2 6.2     14.4 16.6 6.9 5.9 4.5 5.2 6.0 MAJOR COMPONENT, AREA % E-6 E-6 E-6 E-6     E-7 E-6 E-6 E-6 E-6 E-6 C.sub.12-6 -C.sub.14-7, AREA %.sup.l 40.58 39.59     39.46 37.55 35.23 37.05 36.82 39.16 37.50 40.35 C.sub.12-5 -C.sub.14-8,     AREA %.sup.l 69.47 68.81 67.79 65.03 61.47 64.33 64.14 67.28 65.62 68.79 C     a CONTENTS, ppm.sup.m PRODUCT 12 -- 9 -- 9 -- 9 -- 8 -- BY-PRODUCT --     150 -- 120 -- 115 -- 117 -- 116     .sup.a Weight following hot toluene extraction followed by filtration and     RotaVac drying at 110° C., 5-10 mm Hg pressure.     .sup.b I = incremental mode of feed; C = continuous mode of feed.     .sup.c Reaction time shown is to completion of cookout period.     .sup.d Crude net weight obtained by weighing reactor containing product     and subtracting tare weight of reactor.     .sup.e Actual product obtained by filtration plus product extracted from     filter cake.     .sup.f Weight of catalyst after extraction with hot toluene, filtration     and RotaVac drying at 110° C./5-10 mm Hg. In some runs, small     quantities of catalyst were lost in running cloud point tests.     .sup.f *Final catalyst weight recovered from run No. 20 was 16.6 g. after     ordinary extraction procedure. More vigorous extraction for 5.0 hours wit     boiling toluene served to remove only 0.25 g. of material. Final Ca     analysis was 0.12%, equivalent to 0.24% on original dry catalyst basis.     .sup.g Alfol 1214 used as predried over molecular sieves.     .sup.h Alfol 1214 molecular weight of 202 used to calculate this value     from hydroxyl molecular weight figure.     .sup.i By gas chromatography using SP2100 column with ndecanol internal     standard.     .sup.j By titration with 0.01 N alcoholic HCl in 95/5 MeOH/H.sub.2 O usin     bromothymol blue indicator.     .sup.k By room temperature extraction of about 25 gram sample with 225     grams of Et.sub.2 O followed by filtration and drying of solids in vacuum     desiccator overnight.     .sup.l By gas chromatography using SP2100 column.     .sup.m By Industively Coupled Plasma Emission technique.

EXAMPLE 12 Preparation of Poly(oxyethylene)glycols of about 600Molecular Weight

The catalyst used for the preparation of poly(oxyethylene)glycols wasCatalyst H. The unmodified Catalyst H contained 2.95% calcium; it wasused (two separate portions) to carryout 2×5 run sequential batch seriespreparations of poly(oxyethylene)glycols of about 600 molecular weightin a 1-liter stirred autoclave similar to the 300 milliliter and 600milliliter versions described in previous examples. In these experimentsCatalyst H was recovered for recycle by a centrifugation/decantationprocedure which provided a "wet" form for recycle. For seven of theseten runs, the standard charge of diethylene glycol initiator was 35.0grams; for the last three runs, this charge was 32.0 grams. The targetfeed for ethylene oxide was about 163 grams, the theoretical quantitynecessary to advance the diethylene glycol charge to a polymer of about600 molecular weight. Molecular weights attained were invariablysomewhat below theoretical; this was undoubtedly due to the present ofpoly(oxyethylene)glycols absorbed on the catalyst, effectivelyincreasing the quantity of initiating species present. Experimentaldetails and product characterization data are summarized in Tables VIIand VIII below. FIG. 2 depicts the average ethoxylate distribution forpoly(oxyethylene)glycols prepared in series 1 and series 2 of thisexample (supported CaO) as well as unsupported Ca(OH)₂ and unsupportedKOH.

                                      TABLE VII                                   __________________________________________________________________________    RUN SERIES      ONE                                                           RUN NO. IN SERIES                                                                             1    2    3    4    5                                         __________________________________________________________________________    Preparation                                                                   Temperature, °C.,.sup.a                                                                140-160                                                                            140-160                                                                            140-150                                                                            140-175                                                                            140-160                                   Pressure, psig.sup.b                                                                          20-98                                                                              20-98                                                                              20-104                                                                             12-104                                                                             18-104                                    Reactants Weights, g.                                                         Diethylene Glycol                                                                             35.0 35.0 35.0 35.0 35.0                                      Catalyst.sup.d  4.0  9.62 10.95                                                                              12.0 14.01                                     Ethylene Oxide.sup.c                                                                          163.5                                                                              173.2                                                                              163.1                                                                              175.1                                                                              166.8                                     Reaction Time, Hrs. (approx.)                                                                 15   17   23.0 34   57                                        Product Weight, g.                                                                            197.1                                                                              201.3                                                                              198.2                                                                              207.9                                                                              209.0                                     Material Balance %                                                                            97.3 92.4 94.8 93.6 96.8                                      Characterization                                                              Appearance, 25° C.                                                                     v. slushy                                                                          hazy hazy hazy slushy                                                    liq. liq. liq. liq. liq.                                      Molecular Weight, by OH No.                                                                   556.2                                                                              549.7                                                                              529.6                                                                              527.3                                                                              532.2                                     Alkalinity, as CaO, %.sup.e                                                                   0.0423                                                                             0.0058                                                                             0.0031                                                                             0.0017                                                                             0.0012                                    pH, 5% Aqueous Solution                                                                       10.06                                                                              8.35 7.121                                                                              6.92 6.80                                      Viscosity, CKS @ 25° C., 50%                                                           13.1 12.7 12.5 13.0 13.1                                      Aqueous Sol'n.                                                                Absolute Ethanol                                                                              2.8  4.2  2.9  4.6  1.7                                       Insolubles, %.sup.g                                                           Ethoxylate Distribution, Area %.sup.f                                         Pentaethylene Glycol                                                                          --   0.03 0.04 --   --                                        Hexaethylene Glycol                                                                           <0.02                                                                              0.06 0.05 <0.05                                                                              0.1                                       Heptaethylene Glycol                                                                          0.04 0.63 0.43 0.26 0.77                                      Octaethylene Glycol                                                                           1.02 3.37 3.71 1.91 3.93                                      Nonaethylene Glycol                                                                           7.15 8.5  9.55 5.09 9.25                                      Decaethylene Glycol                                                                           15.71                                                                              15.02                                                                              16.04                                                                              13.18                                                                              14.45                                     Undecaethylene Glycol                                                                         21.55                                                                              18.83                                                                              19.33                                                                              15.30                                                                              17.44                                     Dodecaethylene Glycol                                                                         20.94                                                                              18.03                                                                              18.04                                                                              15.11                                                                              16.94                                     Tridecaethylene Glycol                                                                        15.61                                                                              13.94                                                                              13.62                                                                              13.11                                                                              13.73                                     Tetradecaethylene Glycol                                                                      9.48 9.29 8.75 10.38                                                                              9.82                                      Pentadecaethylene Glycol                                                                      4.89 5.68 5.25 8.11 6.55                                      Hexadecaethylene Glycol                                                                       2.33 3.78 3.18 5.35 4.75                                      Heptadecaethylene Glycol                                                                      0.89 1.77 1.35 2.36 2.04                                      Octadecaethylene Glycol                                                                       0.31 0.63 0.52 0.53 0.28                                      Nonadecaethylene Glycol                                                                       <0.1 0.27 0.17 --   0.04                                      __________________________________________________________________________     .sup.a Range experienced; target temperature was 104° C.;              excursions were principally of mechanical malfunction origin.                 .sup.b Ranges shown do not include extreme values experienced during          temperature excursions due to mechanical problems.                            .sup.c Weight indicated by tank readings of weight loss corrected by          occasional actual weight checks.                                              .sup.d Original catalyst change was 4.0 grams; higher weights in              subsequent runs reflect presence of residual products buildup on resin.       .sup.e By titration with 0.01N alcoholic HCl in CELLOSOLVE using              bromothymol blue indicator.                                                   .sup. f Obtained with SP2100 column using Regisil ® derivatized           sample.                                                                       .sup.g Extraction of 25 grams with absolute ethanol at room temperature       followed by filtration evaporation of filtrate.                          

                                      TABLE VIII                                  __________________________________________________________________________    RUN SERIES      TWO                                                           RUN NO. IN SERIES                                                                             1    2    3     4     5                                       __________________________________________________________________________    Preparation                                                                   Temperature, °C.,.sup.a                                                                140-170                                                                            140-165                                                                            140-162.sup.g,h                                                                     140-190.sup.g,h                                                                     140-161.sup.h,i                         Pressure, psig.sup.b                                                                          20-104                                                                             10-104                                                                             12-108                                                                              8-112 9-120                                   Reactants Weights, g.                                                         Diethylene Glycol                                                                             35.0 35.0 32.0  32.0  32.0                                    Catalyst.sup.d  4.0  10.22                                                                              14.4  10.65 12.43                                   Ethylene Oxide.sup.c                                                                          163.6                                                                              165.0                                                                              167.6 173.3 167.4                                   Reaction Time, Hrs. (approx.)                                                                 20   24   26    62    >60                                     Product Weight, g.                                                                            201.5                                                                              207.2                                                                              212.45                                                                              212.27                                                                              208.1                                   Material Balance %                                                                            99.5 98.6 99.3  98.3  98.2                                    Characterization                                                              Appearance, 25° C.                                                                     Slushy                                                                             Hazy Waxy  Slushy                                                                              Hazy                                                    Solid                                                                              Liq. Liq.  Solid Liquid                                  Molecular Weight, by OH No.                                                                   568.4                                                                              558.3                                                                              619.1 550.6 531.9                                   Alkalinity, as CaO, %.sup.e                                                                   0.0564                                                                             0.0074                                                                             0.0025                                                                              0.0008                                                                              0.0006                                  pH, 5% Aqueous Solution                                                                       10.3 9.07 7.1   7.3   7.1                                     Viscosity, CKS @ 25° C., 50%                                                           14.3 13.7 15.1  15.0  14.5                                    Aqueous Sol'n.                                                                Absolute Ethanol                                                                              6.2  4.0  1.5   4.0   2.2                                     Insolubles, %.sup.j                                                           Ethoxylate Distribution, Area %.sup.f                                         Pentaethylene Glycol                                                                          0.21 0.05 --    --    0.02                                    Hexaethylene Glycol                                                                           0.43 0.47 --    0.05  0.03                                    Heptaethylene Glycol                                                                          0.77 0.93 0.30  0.84  1.25                                    Octaethylene Glycol                                                                           2.65 2.80 1.99  3.11  3.11                                    Nonaethylene Glycol                                                                           4.93 6.44 4.46  6.05  6.03                                    Decaethylene Glycol                                                                           12.11                                                                              11.06                                                                              8.02  9.79  9.5                                     Undecaethylene Glycol                                                                         18.45                                                                              14.76                                                                              11.97 13.27 12.65                                   Dodecaethylene Glycol                                                                         20.12                                                                              16.06                                                                              14.80 15.14 14.51                                   Tridecaethylene Glycol                                                                        16.76                                                                              14.98                                                                              15.57 15.02 14.46                                   Tetradecaethylene Glycol                                                                      11.37                                                                              12.30                                                                              14.73 13.46 12.67                                   Pentadecaethylene Glycol                                                                      6.97 9.49 13.03 11.12 9.86                                    Hexadecaethylene Glycol                                                                       3.90 6.03 9.36  7.78  7.04                                    Heptadecaethylene Glycol                                                                      1.58 2.91 4.80  3.84  4.86                                    Octadecaethylene Glycol                                                                       0.38 0.59 0.88  0.53  2.94                                    Nonadecaethylene Glycol                                                                       0.10 --   --    --    0.84                                    __________________________________________________________________________     .sup.a Range experienced; target temperature was 104° C.;              temperature excursions were principally of mechanical modification origin     .sup.b Ranges shown do not include extreme values experienced during          temperature excursions due to mechanical problems.                            .sup.c Weight indicated by tank reading of weight loss corrected by           occasional actual weight checks.                                              .sup.d Original catalyst change was 4.0 grams; higher weights in              subsequent runs reflect presence of residual products buildup on resin.       .sup.e By titration with 0.01N alcoholic HCl in CELLOSOLVE using              bromothymol blue indicator.                                                   .sup.f Obtained with SP2100 column using Regisil ® derivatized            examples.                                                                     .sup.g Major equipment malfunctions during these runs; temperature            exceeded 200° C. at times, especially in case of run number 4.         .sup.h An internal cooling coil was added part way through run 3 and used     thereafter to improve temperature control.                                    .sup.i Catalyst activity was low; catalyst damage was probably sustained      during run #4, or runs 3 and 4.                                               .sup.j Extraction of 25 grams with 250 grams absolute ethanol at room         temperature.                                                             

EXAMPLE 13 Preparation of Poly(oxyethylene)glycols of about 300Molecular Weight

The catalyst for this series of 5 sequential batch preparations wasCatalyst J. The poly(oxyethylene)glycol preparations with Catalyst Jwere carried out in a 1.5 gallon circulated loop type autoclave equippedto automatically feed ethylene oxide as needed to maintain 60 psig. Thestarter for these runs was diethylene glycol (DEG); a typical startercharge was about 500 grams while a typical target quantity of ethyleneoxide was about 915 grams. The catalyst recovery/recycle procedure usedin this series involved filtering the crude reaction product, slurringthe moist recovered catalyst in toluene at 80-90° C., refiltering anddrying in vacuo at 100° C./5 mm Hg. The original catalyst charge for theseries of preparations was 12.0 grams; the final catalyst weight aftercompletion of the series was about 21 grams. Experimental details andpertinent product characterization data for this series of preparationsare given in Table IX below.

                                      TABLE IX                                    __________________________________________________________________________                    RUN NO. IN SERIES                                                             1    2    3    4    5                                         __________________________________________________________________________    Preparative Conditions                                                        Temperature, °C.                                                                       138-142                                                                            140-142                                                                            140-142                                                                            140-143                                                                            139-141                                   Pressure, psig  62.5-64                                                                            61-68                                                                              60-67                                                                              62-66                                                                              61-74                                     Reaction Time, Hrs.                                                                           ˜4                                                                           ˜18                                                                          ˜32                                                                          ˜43                                                                          ˜32                                 Reactants/Weights                                                             Diethylene Glycol                                                                             497  503  500  500  501                                       Ethlyene Oxide  908  914  913  924  912                                       Catalyst        12.0 22.8 25.1 21.8 22.0                                      Product Weight, g.                                                                            1339 1368 1360 1345 1366                                      Material Balance %                                                                            94.5 95.0 94.6 93.0 95.3                                      Product Characterization                                                      Molecular Weight (by OH No.)                                                                  292.1                                                                              300.5                                                                              286.7                                                                              295.0                                                                              302.6                                     Alkalinity, meqs/g.                                                                           0.0129                                                                             0.0018                                                                             0.0007                                                                             0.0001                                                                             0.0007                                    pH, 5% Aqueous Sol'n                                                                          9.95 8.60 7.12 6.41 6.45                                      Mols EO/Mol. DEG.                                                                             4.23 4.43 4.11 4.30 4.47                                      Ethoxylate Distribution, Area %                                               Diethylene Glycol                                                                             --   --   --   --   --                                        Triethylene Glycol                                                                            0.31 0.36 0.98 1.46 0.78                                      Tetraethylene Glycol                                                                          9.11 9.26 10.71                                                                              10.70                                                                              9.56                                      Pentaethylene Glycol                                                                          20.61                                                                              20.61                                                                              20.84                                                                              19.69                                                                              18.68                                     Hexaethylene Glycol                                                                           25.32                                                                              24.78                                                                              23.92                                                                              22.83                                                                              22.59                                     Heptaethylene Glycol                                                                          21.32                                                                              21.04                                                                              20.15                                                                              19.90                                                                              20.45                                     Octaethylene Glycol                                                                           13.58                                                                              13.58                                                                              13.13                                                                              13.56                                                                              14.45                                     Nonaethylene Glycol                                                                           6.76 6.98 6.85 7.47 8.22                                      Decaethylene Glycol                                                                           2.60 2.85 2.86 3.39 3.84                                      Undecaethylene Glycol                                                                         0.40 0.54 0.55 1.00 1.30                                      Dodecaethylene Glycol                                                                         --   --   --   --   0.07                                      __________________________________________________________________________

EXAMPLE 14 Part A. Preparation of Poly(oxyethylene)glycols of about 300Molecular Weight

The catalyst for these two preparations of poly(oxyethylene)glycols ofabout 300 molecular weight was Catalyst K. The reactor for thesepreparations was a 1-liter stirred autoclave equipped with an automaticethylene oxide feed system wherein a motor valve controlled the feed ofethylene oxide to maintain about 60 psig pressure.

The temperature at which these runs were made was 140-148° C.; theinitiator used was ethylene glycol For the first of the twopreparations, 80.0 grams of ethylene glycol was charged along with 8.0grams of Catalyst K. The amount of ethylene oxide fed was 308.2 grams;the reaction time was five hours. For the second preparation, therecovered catalyst (moist, 14.4 grams wet) was charged along with 80.0grams of ethylene glycol and 310 grams of ethylene oxide was fedaccording to weight loss indicated for the oxide feed tank. The reactiontime for this run was about 11 hours. The properties of thepoly(oxyethylene)glycol products are given in Table X below.

                  TABLE X                                                         ______________________________________                                                       Run No. In Series                                                             1        2                                                     ______________________________________                                        Molecular Weight (by OH #)                                                                     284.5      258.7                                             Mols EO/Mol EG   5.06       4.47                                              pH, 5% Aqueous Solution                                                                        9.0        8.75                                              Alkalinity, Meqs/g.                                                                            0.0009     0.0007                                            (by titration)                                                                Calcium content, ppm (by ICPE)                                                                 26         27                                                Color            Straw      Straw                                             Major Component, by GC                                                                         Hexaethylene                                                                             Hexaethylene                                                       Glycol     Glycol                                            Conc. of Major Component,                                                     GC Area %        20.2       20.7                                              ______________________________________                                    

Part B. Preparation of Fatty Alcohol Ethoxylates

The catalyst for these four preparations of C₁₂ /C₁₄ primary alcoholethoxylates was Catalyst L. The exchanged reaction product was strippedfree of most of the excess Alfol 1214 to leave the catalyst as aconcentrated slurry in Alfo1 1214 (89 grams total weight). The 89.0grams of slurry was used as charge for the first ethoxylation in theseries of five. For each of the subsequent runs, the catalyst wasmaterial recovered (by filtration) from the previous run and the Alfol1214 charge was 40.0 grams. The runs were made in the 600 milliliterstirred autoclave described previously. Typical conditions were about140° C. temperature; about 60-80 psig pressure; ethylene oxide feed wasby manual means, increments being fed as convenient to keep pressurewithin the desired range. Pertinent data on these four ethoxylations issummarized in Table XI below; the first preparation in the seriesafforded atypical product because major mechanical problems wereencountered during the run.

                  TABLE XI                                                        ______________________________________                                                        Run No. in Series                                                             1    2       3       4                                        ______________________________________                                        Mols EO/Mol Alfol 1214                                                                          4.25   6.22    6.02  6.25                                   Molecular Weight (by OH No.)                                                                    389.0  475.7   467.2 477.1                                  Cloud Point, °C. (1% Solution)                                                           ˜25                                                                            42      42    50                                     pH, 5% Aqueous Solution                                                                         8.3    7.4     7.35  7.3                                    Alkalinity, meq/g.                                                                              n.d.   0.0005  0.0004                                                                              0.001                                  ______________________________________                                    

EXAMPLE 15 Preparation of Poly(oxyethylene)glycols of about 300Molecular Weight

The catalysts for these two series of poly(oxyethylene)glycolpreparations were Catalyst M and Catalyst N. Both unmodified Catalyst Mand acid-modified Catalyst N were used to conduct 4-run sequential batchpreparations of poly(oxyethylene)glycol products. In both series ofpreparations the reactor was the 600 milliliter stirred autoclavedescribed previously and the initial catalyst charge was 8.5 grams.Diethylene glycol was employed as the initiator, 30.0 grams being thestandard charge for each run. The target quantity of ethylene oxide feedwas about 58.5 grams; temperature and pressure used were 140° C. and 60psig, respectively. The procedure used for recovering/recycling thecatalysts was to filter the crude reaction product, slurry the recoveredcatalyst in hot toluene (80-90° C. two hours), refilter, and dry thesolid in vacuo at ambient temperature. The portion of the liquid productrecovered each time from slurrying the wet catalyst in tolueneinvariably had the same composition (by gas chromatography) as the mainportion of the product obtained from the initial filtration. Tables XIIand XIII below contain pertinent data on these two series ofpoly(oxyethylene)glycol preparations; Table XII covers the experimentscarried out with unmodified Catalyst M and Table XIII the experimentswith acid-modified Catalyst N.

                  TABLE XII                                                       ______________________________________                                                         Run No. In Series                                                             1    2       3      4                                        ______________________________________                                        Molecular Weight (by OH No.)                                                                     340.5  332.9   299.3                                                                              299.3                                  Alkalinity, meqs/g.                                                                              0.009  0.016   0.010                                                                              0.0027                                 pH, 5% Aqueous Solution                                                                          9.7    10.05   9.6  8.0                                    Reaction Time, hours                                                                             5.0    3.1     5.0  14.0                                   Ethoxylate Distribution, Area %                                               Diethylene Glycol  --     --      --   --                                     Triethylene Glycol --     --      0.29 0.31                                   Tetraethylene Glycol                                                                             3.03   4.18    9.44 10.22                                  Pentaethylene Glycol                                                                             10.82  12.86   21.22                                                                              21.80                                  Hexaethylene Glycol                                                                              18.97  20.66   25.16                                                                              24.67                                  Heptaethylene Glycol                                                                             22.38  22.45   20.59                                                                              19.71                                  Octaethylene Glycol                                                                              19.50  18.16   12.86                                                                              12.29                                  Nonaethylene Glycol                                                                              13.35  11.67   6.59 6.39                                   Decaethylene Glycol                                                                              7.47   6.25    2.91 2.96                                   Undecaethylene Glycol                                                                            3.44   2.85    0.95 1.27                                   Dodecaethylene Glycol                                                                            1.05   0.92    --   0.39                                   ______________________________________                                    

                  TABLE XIII                                                      ______________________________________                                                        Run No. In Series                                                             1     2       3      4                                        ______________________________________                                        Molecular Weight, (by OH No.)                                                                   371.0.sup.a                                                                           294.5   312.7                                                                              323.6.sup.a                            Alkalinity, meqs/g.                                                                             0.0173  0.0029  0.001                                                                              0.0009                                 pH, 5% Aqueous Solution                                                                         10.01   8.50    7.05 7.36                                   Reaction Time, Hours                                                                            3.4     5.75    8.75 9.0                                    ______________________________________                                         .sup.a Unintentional overfeed of ethylene oxide accounts for high             molecular weight.                                                        

EXAMPLE 16 Preparation of Poly(oxyethylene)glycols of about 200Molecular Weight

The catalyst used for making this series o 8 sequential runs wasCatalyst P. The poly(oxyethylene)glycol preparation carried-out usingmodified Catalyst P comprised a series of 8 sequential batch runs in the600 milliliter stirred autoclave described previously. The initiator forthese runs was ethylene glycol; the standard initiator charge was 31.0grams and the target quantity of ethylene oxide was 69.8 grams in eachrun. Catalyst P was used in an initial quantity of 7.5 grams; subsequentruns employed recycled catalyst obtained by filtering the reactionproduct, slurrying the recovered catalyst in hot toluene, refiltering,and finally drying the recovered solid catalyst in vacuo at 85°C./.sup.˜ 5 mm Hg pressure. Following this procedure, the weight ofdried catalyst recovered after the 8th and final batch run was 7.7grams; the calcium and sulfur contents were 0.18 and 0.1%, respectively.Table XIV below contains pertinent data on characterization of thepoly(oxyethylene)glycol products made in this experiment.

                                      TABLE XIV                                   __________________________________________________________________________                      Run No. In Series                                                             1   2   3   4   5   6   7   8                               __________________________________________________________________________    Molecular Wt. by OH No.                                                                         199.2                                                                             201.9                                                                             206.3                                                                             196.6                                                                             188.7                                                                             194.1                                                                             194.7                                                                             199.4                           Alkalinity, meqs/g.                                                                             0.0074                                                                            0.0038                                                                            0.0019                                                                            0.0008                                                                            0.0004                                                                            0.0005                                                                            0.0006                                                                            0.0002                          pH, 5% Aqueous Sol'n                                                                            8.30                                                                              7.33                                                                              7.30                                                                              7.42                                                                              6.96                                                                              7.09                                                                              7.11                                                                              6.50                            Reaction Time, hours                                                                            4.0 6.5 11.75                                                                             15.25                                                                             12.0                                                                              11.75                                                                             12.25                                                                             16.25                           Calcium Content in                                                                              143 33  19  14  2.8 2.2 1.4 0.4                             Product, ppm                                                                  Ethoxylate Distribution, GC Area %                                            Ethylene Glycol   0.44                                                                              0.13                                                                              --  0.14                                                                              0.99                                                                              0.82                                                                              1.16                                                                              2.24                            Diethylene Glycol 0.73                                                                              0.21                                                                              0.10                                                                              0.47                                                                              6.75                                                                              4.82                                                                              5.75                                                                              8.12                            Triethylene Glycol                                                                              26.88                                                                             23.75                                                                             21.84                                                                             30.45                                                                             39.37                                                                             29.27                                                                             27.60                                                                             25.33                           Tetraethylene Glycol                                                                            43.30                                                                             43.17                                                                             44.11                                                                             41.09                                                                             32.21                                                                             31.83                                                                             30.37                                                                             28.12                           Pentaethylene Glycol                                                                            20.89                                                                             22.53                                                                             23.57                                                                             19.09                                                                             14.23                                                                             19.46                                                                             19.58                                                                             19.61                           Hexaethylene Glycol                                                                             6.13                                                                              7.28                                                                              7.71                                                                              6.40                                                                              5.06                                                                              9.17                                                                              9.82                                                                              10.55                           Heptaethylene Glycol                                                                            1.21                                                                              1.87                                                                              2.04                                                                              1.86                                                                              1.39                                                                              3.50                                                                              4.03                                                                              4.56                            Octaethylene Glycol                                                                             0.05                                                                              0.45                                                                              0.51                                                                              0.47                                                                              --  0.95                                                                              1.36                                                                              1.48                            Nonaethylene Glycol                                                                             --  --  --  --  --  --  0.14                                                                              --                              __________________________________________________________________________

Although the invention has been illustrated by the preceding examples,it is not to be construed as being limited thereby; but rather, theinvention encompasses the generic area as hereinbefore disclosed.Various modifications and embodiments can be made without departing fromthe spirit and scope thereof.

We claim:
 1. A method for providing an alkoxylation catalystcomprising:(a) preparing a catalyst precursor by reacting an organicpolymer which has a crosslinked and microporous, macroporous orphysically expanded structure with a carbocyclic or heterocycliccompound; (b) solubilizing, at least partially, calcium oxide, calciumhydroxide, or mixtures thereof, by mixing any of them with an activatorhaving the formula

    Z.sub.a --X--Q--Y--Z'.sub.b

wherein X and Y are the same or different electronegative, hetero-atomsselected from the group consisting of oxygen, nitrogen, sulfur andphosphorus; a and b are the same or different integers satisfying thevalency requirements of X and Y; Q is an organic radical which iselectropositive or essentially neutral relative as to X and/or Y; Z andZ' are the same or different and are either hydrogen or an organicradical which does not prevent said solubilizing, thereby forming acalcium-containing, composition which has titratable alkalinity; and (c)reacting the catalyst precursor with the calcium-containing compositionunder effective reaction conditions to chemically bond the calcium atomto the polymer through a carbocyclic or heterocyclic linkage.
 2. Themethod of claim 1 wherein the organic polymer is a polystyrenic polymeror a phenolic polymer.
 3. The method of claim 1 wherein the organicpolymer is a copolymer of styrene and divinyl benzene.
 4. The method ofclaim 1 wherein the organic polymer is a chloromethylatedstyrene/divinyl benzene polymer.
 5. The method of claim 1 wherein thecarbocyclic or heterocyclic compound is of the monocyclic or polycyclictype.
 6. The method of claim 1 wherein the carbocyclic or heterocycliccompound provides an aryloxy or arylthio functional group having a pKain the range of 7-13.
 7. The method of claim 1 wherein the activator hasthe formula: ##STR7## wherein R₆, R₇, R₈ and R₉ are the same ordifferent and are selected from the group consisting of hydrogen andlower alkyl or alkylene groups of one to four carbon atoms.
 8. Themethod of claim 1 wherein the activator is ethylene glycol.
 9. Themethod of claim 1 wherein the activator is 2-ethoxyethanol.
 10. Themethod of claim 1 comprising the additional step of reacting thealkoxylation catalyst with an alcohol under conditions at which analcohol exchange reaction occurs with the alkoxylation catalyst, therebyproducing a corresponding alcohol derivative.
 11. The method of claim 10wherein the alcohol is n-dodecanol.
 12. The method of claim 10 whereinthe alcohol is a mixture of C₁₂ and C₁₄ alcohols.
 13. The method ofclaim 1 comprising the additional step of removing some or all activatorwhich is not bound to calcium.
 14. A method of claim 1 comprising theadditional step of adding a sufficient amount of a polyvalent, oxy acidor a metal salt thereof to neutralize a portion of the titratablealkalinity sufficient to enhance the selectivity of the catalyst.
 15. Amethod of claim 10 comprising the additional step of adding a sufficientamount of a polyvalent, oxy-acid or a metal salt thereof to neutralize aportion of the titratable alkalinity sufficient to enhance theselectivity of the catalyst.
 16. The method of claim 14 wherein theoxy-acid is sulfuric acid.
 17. The method of claim 16 wherein about 25to about 75% of the titratable alkalinity is neutralized.
 18. The methodof claim 16 wherein about 40 to about 60% of the titratable alkalinityis neutralized.
 19. An alkoxylation catalyst having the formula:

    R.sub.1 --R.sub.2 --X.sub.1 --Ca--X.sub.2 --R.sub.3

wherein: R₁ is an organic polymeric residue which has a crosslinked andmicroporous, macroporous or physically expanded structure; R₂ is acarbocyclic or heterocyclic residue; X₁ and X₂ are independently oxygenor sulfur; and R₃ is hydrogen or an organic residue of an organiccompound having at least one active hydrogen.
 20. The alkoxylationcatalyst of claim 19 in which said catalyst is reacted with an alcoholunder conditions at which an alcohol exchange reaction occurs with thecatalyst, thereby producing a corresponding alcohol derivative.
 21. Thealkoxylation catalyst of claim 19 in which a sufficient amount of apolyvalent, oxy-acid or a metal salt thereof is reacted with saidcatalyst to neutralize a portion of the titratable alkalinity sufficientto enhance the selectivity of the catalyst.
 22. An alkoxylation catalystprepared by the method of claim
 1. 23. An alkoxylation catalyst preparedby the method of claim
 10. 24. An alkoxylation catalyst prepared by themethod of claim
 14. 25. An alkoxylation catalyst prepared by the methodof claim 15.